CZ287405B6 - Process for preparing catalyst system and use thereof - Google Patents

Abstract

In the present invention there is disclosed a process for preparing a catalyst system which preparation process is characterized by connecting a metal source, a pyrrole-containing compound and an alkyl metal in a common solvent without previous reaction stage between the metal source and the pyrrole-containing compound in the presence of an electron-donating solvent. The preparation can be optionally carried out in the presence of an unsaturated hydrocarbon. A chromium, nickel, cobalt, iron, molybdenum or copper compound, particularly chromium compound, can preferably represent the metal source. The pyrrole-containing compound can be preferably represented by pyrrole or 2,5-dimethylpyrrolide and the alkyl metal can be preferably represented by aluminium, lithium, magnesium or zinc derivative, particularly aluminium derivative. When preparing this system also a carried may be added and the preparation can be carried out in the presence of a halide. In the present invention there is also claimed the use of so prepared catalyst system for trimerization, oligomerization or polymerization of an olefinic compound.

Description

Process for the preparation of a catalyst system and its use

Technical field

The present invention relates to a catalyst system and its use for the trimerization, oligomerization or polymerization of olefins.

BACKGROUND OF THE INVENTION

Catalysts based on metal oxide, in particular supported chromium, play a major role in the production of olefin polymers such as polyethylene, or copolymers of ethylene and hexene. These catalysts can be used in a variety of polymerization processes. However, the most known chromium compounds must be supported on the support to be catalytically active. In addition, most supported chromium compounds are only suitable for olefin polymerization. If an olefin copolymer is desired, the polymerization process is more complicated in that two different monomers must be introduced into the polymerization reactor.

The olefin trimerization and oligomerization catalysts are also known in the art, but usually do not show selectivity to the desired product and also provide a low product yield. However, if the trimerization and / or oligomerization of olefins is effected efficiently, useful olefins can be obtained. These olefinic products may be further trimerized, oligomerized and / or optionally incorporated into the polymerization process.

EP-A-416 304 discloses a chromium-containing compound having the following formula:

Cr (CH ₄ NH ₄ ) 3 / (Cr (C ₄ H ₄ N) 4 / Na / ₂ .2 (OC ₄ H ₃ ), (CrC ₄ H ₄ N ₄ O ₄ ) / Na / M 1 O 2) or Cr (NC ₄ H ₄ ) ₃ Cl (O ₂ C) ₂ H4 (CH3) ₂ ) 3Na.

According to the above-cited application, novel chromium-containing compounds are prepared from a reaction mixture including a chromium salt, a metal amide, and any electron pair donor solvent, such as an ether. The catalyst system can be used either on a support or not on a support for trimerization and / or polymerization of olefins.

The chromium salt may be one or more organic or inorganic chromium salts in which the chromium oxidation degree is from 0 to 6. In this specification, chromium metal is included in the definition of the chromium salt. Generally, the chromium salt will have the formula CrX _n , where X may be the same or different and may be any organic or inorganic radical and n is an integer from 1 to 6. Examples of organic radicals may have from about 1 to about 20 carbon atoms per radical and may be selected from the group consisting of alkyl, alkoxy, ester, ketone and / or amidoradicals. The organic radicals may be straight chain or branched, cyclic or acyclic, aromatic or aliphatic, and may be prepared from mixed aliphatic, aromatic and / or cycloaliphatic groups. Examples of inorganic radicals include, but are not limited to, halides, sulfates and / or oxides.

Preferably, the chromium salt is a halide such as chromium fluoride, chromium fluoride, chromium chloride, chromium chloride, chromium bromide, chromium bromide, chromium iodide, chromium iodide and mixtures thereof. Most preferably, the chromium salt is a chloride such as chromium (III) chloride and / or chromium (III) chloride due to the simple separation of by-products such as sodium chloride, as well as due to the relatively low cost.

The metal amide may be any metal amide that will react with the chromium salt to form a chromium-amide complex. More broadly, the metal amide may be any heteroleptic or homoleptic metal complex or salt, wherein the amide residue may be any nitrogen

Containing an organic residue. The metal amide can either be added to the reaction or generated in situ. Generally, the metal amide will have from about 1 to about 20 carbon atoms.

Examples of suitable metal amides include, but are not limited to, lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, lithium dicyclohexylamide, bis (trimethylsilyl) amide, sodium indolide, alkali metal and alkaline earth metal pyrrolides, and mixtures of two or more of the above compounds. Most preferred are the above-mentioned metal pyrrolides, such as lithium pyrrolidide, sodium pyrrolidide, potassium pyrrolidide and cesium pyrrolidide, for their high reactivity and activity with other reactants. Examples of substituted pyrrolides include, but are not limited to, sodium 2,5-dimethylpyrrolidide and / or sodium 3,4-dimethylpyrrolidide. When the metal amide is a pyrrolidide ligand, the resulting metal compound is chromium pyrrolidine.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a catalyst system comprising combining a metal source, a pyrrole-containing compound and an alkyl metal in a co-solvent without a prior reaction step between the metal source and the pyrrole-containing compound in the presence of an electron donor solvent.

In one specific embodiment of the process of the invention, an unsaturated hydrocarbon is optionally added during the preparation, optionally providing a co-solvent. As the unsaturated hydrocarbon, an aromatic or aliphatic hydrocarbon having less than 70, preferably less than 20 carbon atoms per molecule is preferably used. A suitable aromatic hydrocarbon is, for example, toluene, benzene, xylene, mesitylene or hexamethylbenzene. The excess unsaturated aromatic hydrocarbon is preferably removed from the resulting catalyst system by evaporation. A suitable aliphatic unsaturated hydrocarbon is, for example, ethylene.

In preferred embodiments of the invention, the chromium, nickel, cobalt, iron, molybdenum or copper compound is used as the metal source, especially the chromium compound, the pyrrole-containing compound is pyrrole or 2,5-dimethylpyrrolidone and the alkyl metal is an aluminum, lithium, magnesium derivative. or zinc, preferably an alkyl aluminum, especially a trialkyl aluminum compound such as triethyl aluminum.

According to another preferred embodiment, a carrier such as an inorganic oxide is also introduced into the catalyst system. As inorganic oxide, preference is given to silica, combined silica-alumina, alumina, fluoridated alumina, silated alumina, thorium oxide, aluminophosphate, aluminum phosphate, phosphated silica, phosphated alumina, combined silica-titanium dioxide, co-precipitated silica / titanium dioxide, fluoridated / silated alumina or mixtures thereof.

According to a further preferred embodiment of the process according to the invention, the preparation is carried out in the presence of an added halide source, for example a chloride or bromide source or a mixture thereof. As a halide source, a compound of the formula R _m X _n is preferably used, wherein R is an organic or inorganic residue, X is a halide, and the sum of m plus n is any number greater than zero. For example, it may be aluminum, silicon, germanium, hydrogen, boron, lithium, tin, gallium, indium, lead or a mixture thereof, especially tin, germanium or a mixture thereof.

The resultant catalyst system obtained by the process of the invention preferably has the following relative ratio of components (a) 1 mol of metal source metal, (b) 1 to 15 mol of pyrrole-containing compound, (c) 5 to 40 mol alkyl and, if present,

(D) 1 to 30 moles of halide.

The whole process according to the invention is preferably carried out with the exclusion of oxygen and water.

According to one preferred embodiment of the process of the invention, the metal source and the pyrrole-containing compound are combined prior to the addition of the alkyl metal.

The catalyst system prepared by the process of the invention may be prepared as a cocatalyst system which is further combined with the polymerization catalyst system itself, for example a catalyst comprising chromium, titanium, zirconium and / or vanadium.

The invention also relates to the use of a catalyst system or a catalyst / cocatalyst system prepared by the process according to any of the preceding claims for trimerization, oligomerization or polymerization of an olefinic compound. The olefinic compound used preferably has from 2 to 30 carbon atoms per molecule and at least one olefinic double bond. Examples of preferred olefinic compounds include ethylene, 1-butene, 1-hexene, 1,3-butadiene or a mixture thereof.

If an unsaturated hydrocarbon is added in the preparation of the catalyst system, the unsaturated hydrocarbon may, according to one preferred embodiment, be introduced for the first time during the trimerization, oligomerization or polymerization process. The unsaturated hydrocarbon used to prepare the catalyst system may be an unsaturated aliphatic hydrocarbon which also acts as an olefinic compound which is trimerized, oligomerized or polymerized.

The following description is particularly directed to embodiments of the invention in which a chromium source is used as the metal source.

Ether may be used as the electrondonomic solvent in the process of the invention. The ether in the reaction mixture may be one or more ether compounds for an effective reaction between a metal salt and a pyrrole-containing compound, preferably a chromium salt and a metal pyrrolide. Without wishing to be bound by theory, it is believed that the ether may be a reaction solvent as well as a possible reactant. The ether may be any aliphatic and / or aromatic compound containing the R-O-R function, wherein the R groups may be the same or different, but preferably are not hydrogen. Preferred ethers are aliphatic ethers, which are more advantageous in terms of safety since aromatic ethers are human poisons. Further preferred are those ethers which facilitate the reaction between the chromium halide and the metal pyrrolidide of the IA group or the ILA group and can also be easily removed from the reaction mixture. Examples of such compounds include, but are not limited to, tetrahydrofuran, dioxane, diethyl ether, dimethoxyethane (glyme), diglyme, triglyme, and mixtures of two or more thereof. Most preferably, the ether is selected from the group consisting of tetrahydrofuran, tetrahydrofuran derivatives, dimethoxyethane, dimethoxyethane derivatives and mixtures thereof for the above reasons, and for this reason that the preferred amine salt is soluble in these ethers.

The three reactants may be combined in any manner under conditions suitable to form a solution containing one or more of the chromium compounds of the invention. The reaction is preferably carried out in the absence of oxygen and moisture and therefore under an inert atmosphere such as nitrogen and / or argon. The reaction pressure may be any pressure sufficient to maintain the reactants in a liquid state. Generally, pressures from about atmospheric pressure to about 3 atmospheres are acceptable. In general, atmospheric pressure is easily used.

The precipitated chromium compounds can be isolated by any method known in the art. The simplest way to remove precipitated compounds is to chrome filtration.

The metal pyrrolides as catalyst or cocatalyst can also be prepared from metal salts other than chromium according to the invention. Examples of metals include nickel, cobalt, iron, molybdenum and copper. As with the chromium salt, the metal oxidation step can be any oxidation step, including a metal

-3GB 287405 B6 in elementary, ie metal, state. These new metal pyrrolides can be prepared similarly to chromium pyrrolides.

The chromium or other metal compounds prepared by the above process can be used as a supported and / or unsupported catalyst system for trimerization, oligomerization and / or polymerization. A catalyst system with a metal, preferably chromium supported on a support, can be prepared with any support that is generally suitable for this purpose. Examples of carriers include, but are not limited to, zeolites, inorganic oxides either alone or in combination, phosphated inorganic oxides, and mixtures thereof. Particularly preferred are carriers selected from the group consisting of silica, silica-alumina, alumina, fluorinated alumina, silated alumina, thorium oxide, aluminophosphates, aluminum phosphate, phosphated silica, phosphated alumina, silica-titanium dioxide , co-precipitated silica / titanium dioxide, fluoride / silated alumina and mixtures thereof, some of which are particularly preferred, as well as any one or more of these carriers which may contain chromium. The most preferred catalyst carrier for its greatest trimerization activity is aluminophosphate as disclosed in U.S. Patent 4,364,855 (1982).

The amount of the chromium pyrrolid compound per gram of carrier can be expressed in different but equivalent terms, for example as mol of chromium per gram of carrier. Typically less than 8.6 x 10 ^-3 moles of chromium per gram of carrier are sufficient. Preferably, about 1.7 x 10 ^-6 to about 1.7 x 10 ^-5 to 8.6 x 1 (Γ * mol of chromium per gram of carrier is used, for the above advantages).

After addition of the carrier and careful association with the chromium pyrrolide, it can be separated by filtration, vacuum dried, then an activating compound, usually a solution of one or more Lewis acids and / or metal alkyls, preferably in a hydrocarbon solvent, is added to the chromium carrier / pyrrolide mixture. The active supported catalyst system is then separated by filtration. In this specification, a Lewis acid is defined as any compound that is an electron acceptor. Preferably, the activating compound is a compound that can be considered both a Lewis acid and an alkyl metal. As described in greater detail, the activating compound may have any number of carbon atoms. For commercial availability and ease of use, the activating compound will normally contain less than about 70 carbon atoms per metal alkyl molecule and preferably less than about 20 carbon atoms per molecule. Preferred activating compounds including metal alkyl and Lewis acid are, but are not limited to, alkyl aluminum compounds, alkyl boronic compounds, alkyl magnesium, alkyl zinc and / or alkyl lithium compounds. Examples of metal alkyls include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, diethylmagnesium, dibutylmagnesium, diethylzinc, triethylaluminum, trimethylaluminum, triisobutylaluminum, and mixtures thereof. Most preferably, the activating compounds are selected from the group consisting of non-hydrolysed, i.e., not previously contacted with water, alkylaluminum compounds, halogenated alkylaluminum compounds, and mixtures thereof for improved product selectivity, as well as improved catalyst system reactivity, activity and / or productivity. Examples of compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, ethylaluminum sesquioxide, and mixtures thereof for the best catalyst system activity and product selectivity. The most preferred alkylaluminum compound is triethylaluminum for best results in catalyst system activity and product selectivity.

Any amount of activating compound, such as a metal alkyl and / or Lewis acid, is sufficient to activate and / or react with the chrompyrrolidide catalyst. Typically, about 200 g of activating compound, i.e., alkyl metal and / or Lewis acid per gram of chromium, may be used. Preferably, about 1 to about 100 grams of activating compound such as an alkyl metal and / or Lewis acid per gram of chrompyrrolid is used, and most preferably about 5 to about 30 grams of activating compound such as an alkyl metal and / or Lewis acid per gram of chrompyrrolid are used for best catalyst activity. However, the amount of activating compound, such as an alkyl metal and / or Lewis acid, to be used may vary with the catalyst carrier used. For example, if the carrier is silica and / or alumina, too much alkyl metal may be present

And / or Lewis acids reduce the activity of the catalyst. However, the same amount of activating compound as the alkyl metal and / or Lewis acid used with aluminum phosphate does not always significantly reduce the activity of the catalyst.

As described in greater detail herein, the hydrocarbon compound used as solvent may be a combination of one or more aromatic or aliphatic unsaturated hydrocarbon compounds. Without being bound by theory, it is believed that the unsaturated hydrocarbon compound acts more than a solvent and may be a reactant and / or a stabilizing component during and / or after the formation of the catalyst system of the invention. Examples of unsaturated hydrocarbon compounds can be, for example, any unsaturated hydrocarbon compound that can dissolve the activating compound, i.e. wherein the activating compound can be a Lewis acid and / or an alkyl metal, as a solvent. According to this third aspect of the present invention, in addition to aromatic compounds having from about 6 to about 50 carbon atoms per molecule as a solvent as described in the above application, unsaturated aliphatic hydrocarbons having less than about 20 carbon atoms per molecule can be used herein. Specific examples of unsaturated aliphatic compounds include ethylene, 1-hexene, 1,3-butadiene and mixtures thereof. The most preferred unsaturated aliphatic hydrocarbon compound is ethylene because it eliminates the step of preparing the catalyst system and ethylene can be trimerized and / or oligomerized as a reactant. Specific examples of unsaturated aromatic hydrocarbon compounds include, but are not limited to, toluene, benzene, xylene, mesitylene, hexamethylbenzene, and mixtures thereof. As described in our above-mentioned application, the most preferred aromatic hydrocarbon compound is toluene for ease of removal and minimal interference with the resulting catalyst system.

The unsaturated hydrocarbon compound may be present either during the initial contact of the chrompyrrolidide and the activating compound, ie prior to introduction into the trimerization, oligomerization and / or polymerization reactor, or the unsaturated hydrocarbon compound may be introduced directly into the reactor. As mentioned above, one or more olefin reactants may be considered as unsaturated hydrocarbons. Preferably, the unsaturated hydrocarbon is present during the initial contact of the chrompyrrolidide and the activating compound in order to stabilize the resulting catalyst system. In the absence of an unsaturated hydrocarbon, the resulting catalyst system can be deactivated and lose activity over time.

If any amount of hydrocarbon compound is used, if it is too large or too small, it may adversely affect the activity of the catalyst system. Therefore, preferably, the resulting catalyst system is free of excess unsaturated aromatic hydrocarbon. Removal of excess unsaturated aromatic hydrocarbon may be accomplished by any method known in the art such as, for example, any method for solvent removal. Examples of such methods include, but are not limited to, filtration, vacuum drying, inert atmosphere drying, and combinations thereof. Without wishing to be bound by theory, it is believed that removal of the unsaturated hydrocarbon can stabilize the resulting catalyst system. In the absence of a hydrocarbon, it is believed that the catalyst system may lose activity.

An alternative and then preferred method in accordance with the above-mentioned application for the production of a supported catalyst system is the coupling of one or more solid chrompyrrolides of the invention with an unsaturated hydrocarbon solvent as described herein, including, for example, toluene and / or ethylene and an activating compound. as previously described, such as an alkyl metal and / or Lewis acid such as, for example, triethylaluminum.

According to a fourth aspect of the present invention, the catalyst system may be prepared by combining a metal source, a pyrrole-containing compound and an alkyl and preferably unsaturated hydrocarbon compound, in a mutual solvent, without a prior reaction step using an electron donating solvent (for reaction between the metal source and pyrrole containing). compound as described above). A preferred unsaturated hydrocarbon, for example toluene, may serve as a mutual solvent. In the absence of such an unsaturated hydrocarbon

For example, cyclohexane may be used. The catalyst system may further comprise a catalyst carrier. A preferred metal source is a chromium source, but any of the above metals may be used.

The chromium source, similar to the previously mentioned chromium salt, may be one or more organic or inorganic chromium compounds wherein the chromium oxidation state is from 0 to 6. As used herein, metallic chromium is included in this definition of chromium salt. Generally, the chromium source may have the formula CrX _n , where X may be the same or different and may be any organic or inorganic radicals and n is an integer from 1 to 6. Examples of organic radicals may have from about 1 to about 20 carbon atoms per radical and are selected from the group consisting of alkyl, alkoxy, ester, ketone and / or amidoradicals. The organic radicals may be straight-chain or branched, cyclic or acyclic, aromatic or aliphatic, may contain mixed aliphatic, aromatic and / or cycloaliphatic groups. Examples of inorganic radicals include, but are not limited to, halides, sulfates and / or oxides.

Preferably, the chromium source is a divalent and / or trivalent chromium compound that provides a catalyst system with improved trimerization activity. Most preferably, the chromium source is a trivalent chromium compound for ease of use, availability and increased activity of the catalyst system. Examples of chromite compounds include, but are not limited to, chromium carboxylates, chromium naphthenates, chromium halides, chromium pyrrolides and / or chromium dionates. Specific examples of chromite compounds include, but are not limited to, chromium (III) -2,2,6,6-tetramethylheptanedione (Cr (TMHD) ₃ ), chromium (III) -2-ethylhexanoate (Cr (CD) ₃ ), chromium (III) naphthenate / Cr (Np) ₃ /, chromium (III) chloride, chromium (III) tris (2-ethylhexanoate), chromium bromide, chromium chloride, chromium fluoride, chromium (III) oxy-2-ethylhexanoate, chromium (III) dichloroethylhexanoate, chromium (III) acetylacetonate, chromium (III) acetate, chromium (III) butyrate, chromium (III) neopentanoate, chromium (III) laurate, chromium (III) stearate, chromium (III) pyrrolid (s) and and / or chromium (III) oxalate.

Specific examples of chromium (II) compounds include, but are not limited to, chromium fluoride, chromium chloride, chromium bromide, chromium iodide, chromium (II) bis (2-ethylhexanoate), chromium (II) acetate, chromium (II) butyrate, chromium (II) neopentanoate, chromium (II) laurate, chromium (II) stearate, chromium (II) pyrrolides and / or chromium (II) oxalate.

The pyrrole-containing compound can be any pyrrole-containing compound that will react with the chromium salt to form the chrompyrrolidide complex. As used herein, the term "pyrrole-containing compound" means hydrogenpyrrolides, i.e. pyrrole (C ₄ H ₅ N), derivatives of hydrogenpyrrolides as well as pyrrolidide-metal complexes. The "pyrrolid" (or "pyrrole" according to the first aspect of the invention) can be any compound containing a 5-membered nitrogen-containing heterocycle, such as pyrrole, pyrrole derivatives and mixtures thereof. In a broader sense, the pyrrole-containing compound may be pyrrole and / or any heteroleptic or hemoleptic metal complex or salt containing a pyrrolidine radical or ligand. The pyrrole-containing compound can either be added to the reaction or generated in situ. Generally, a pyrrole-containing compound may have about 1 to about 20 carbon atoms per molecule. Examples of pyrrolides (or pyrroles) include hydrogenpyrrolidide (pyrrole), pyrrole derivatives, substituted pyrrolides (or pyrroles), lithium pyrrolides, sodium pyrrolides, potassium pyrrolides, cesium pyrrolides and / or substituted pyrrolides salts, due to high reactivity and activity with other reactants. Examples of substituted pyrrolides (or pyrroles) include, but are not limited to, pyrrole-2-carboxylic acid, 2-acetylpyrrole, pyrrole-2-carboxaldehyde, tetrahydroindole, 2,5-dimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3-acetyl- 2,4-dimethylpyrrole, ethyl 2,4-dimethyl-5- (ethoxycarbonyl) -3-pyrropropionate, ethyl 3,5-dimethyl-2-pyrrole-carboxylate. If the pyrrole-containing compound contains chromium, the resulting chromium compound may be called chrompyrrolidine.

The most preferred pyrrole-containing compounds used in the trimerization catalyst system are selected from the group consisting of hydrogenpyrrolidine, i.e. pyrrole (C ₄ H ₅ N) and / or 2,5-dimethylpyrrole. While all pyrrole-containing compounds can produce high catalysts

By using activity and productivity, using pyrrole and / or 2,5-dimethylpyrrole, a catalyst system can be obtained with increased activity and selectivity to the desired trimerization product, such as trimerization of ethylene to 1-hexene, as well as reduced polymer production.

The alkyl alkyl, also referred to recently as the activating compound, can be any heteroleptic or homoleptic alkyl-metal compound. One or more of such compounds may be used. The ligand (s) on the metal may be aliphatic and / or aromatic. Preferably, the ligand (s) are any saturated or unsaturated aliphatic radicals. The alkyl metal may have any number of carbon atoms. For commercial availability and ease of use, however, alkyls will usually contain less than about 70 carbon atoms per molecule and preferably less than about 20 carbon atoms per molecule. Preferred alkyls include, but are not limited to, alkyl aluminum compounds, alkyl boron compounds, alkyl magnesium compounds, alkyl zinc compounds, and / or alkyl lithium compounds. Examples of alkylmetals include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, diethylmagnesium, diethylzinc, triethylaluminum, trimethylaluminum, triisobutylaluminum, and mixtures thereof.

Most preferably, the activating compounds are selected from the group consisting of non-hydrolysed, i.e., water-free, alkylaluminum compounds, alkylaluminum compound derivatives, halogenated alkylaluminum compounds, and mixtures thereof for improved product selectivity as well as improved catalyst system reactivity, activity and / or productivity. Examples of such compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof for the best catalyst system activity and product selectivity. The most preferred alkylaluminum compound is triethylaluminum for the best results in catalyst system activity and product selectivity as well as commercial availability.

If the desired product trimerization catalyst system must be activated compound at least one non-hydrolyzed alkylaluminum compound, expressed by the general formula A1R _3, A1R ₂ X A1RX ₂ A1R ₂ OR, A1RXOR and / or A1 ₂ R ₃ X _3, wherein R is an alkyl and X is a halogen atom. Examples of compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, diethylaluminum phenoxide, ethylaluminum ethoxy chloride and / or ethylaluminum sesquichloride. Preferably, the activating compound for a trimerization catalyst system is a trialkylaluminum compound, A1R _3, for the above reasons. The most preferred trialkylaluminum compound is triethylaluminum, for the above reasons.

The formation of a stable and active catalyst system can be carried out in the presence of an unsaturated hydrocarbon. As discussed in the previous embodiment, the unsaturated hydrocarbon may be present either during the initial contact of the chromium source, the pyrrole-containing compound and the alkyl metal, or introduced into the trimerization, oligomerization and / or polymerization reactor. In addition, one or more olefin reactants may be considered as an unsaturated hydrocarbon.

Any aromatic or aliphatic hydrocarbon may be used. Preferably, the unsaturated hydrocarbon is present initially in the reaction mixture, and most preferably an aromatic hydrocarbon and / or ethylene is initially present to prepare the highly active catalyst in terms of activity and selectivity, as well as the stability of the catalyst system. The unsaturated hydrocarbon may have any number of carbon atoms per molecule. Typically, the unsaturated hydrocarbon will contain less than about 70 carbon atoms per molecule, preferably less than about 20 carbon atoms per molecule, for commercial availability and ease of use.

The unsaturated hydrocarbon may be gaseous, liquid or solid. Preferably, in order to contact and mix the chromium salt, the pyrrole-containing compound and the alkyl metal, the unsaturated hydrocarbon will be liquid and / or dissolved. Examples of unsaturated aliphatic hydrocarbons include but are not limited to

Ethylene, 1,3-butadiene and mixtures thereof. The most preferred unsaturated aliphatic hydrocarbon is ethylene since it may be a reactant during trimerization (as well as during oligomerization and / or polymerization). Examples of unsaturated aromatic hydrocarbons include, but are not limited to, toluene, benzene, xylene, mesitylene, hexamethylbenzene, and mixtures thereof. Unsaturated hydrocarbons are preferred to improve the stability of the catalyst system as well as to improve the activity of the catalyst system. The most preferred unsaturated aromatic hydrocarbon is toluene for the best stability and activity of the catalyst system.

If the unsaturated aromatic hydrocarbon is added before the introduction of the chromium compounds (s) into the trimerization, oligomerization and / or polymerization reactor, the unsaturated aromatic hydrocarbon is removed or distilled off prior to the introduction of the chromium compounds (s) into the reactor, which may improve catalyst system activity and / or product selectivity. Removal of the unsaturated aromatic hydrocarbon can be accomplished by any method known in the art, such as rapid withdrawal or evaporation. The resulting product is a concentrated or saturated solution of the catalyst system of the invention.

If the unsaturated aromatic hydrocarbon is removed prior to introduction into the reactor, the concentrated or saturated catalyst system of the invention can be dissolved in a solvent compatible with the trimerization, oligomerization and / or polymerization process to improve ease of handling the catalyst system of the invention. Generally, the solvent is the same as the diluent in the reactor. Preferred solvents include, but are not limited to, cyclohexane, isobutane, hexane, pentane, and mixtures thereof.

The reaction can also advantageously be carried out in the presence of a halide source. The presence of a halide source can increase catalyst system activity and productivity as well as increase product selectivity. Examples of halides include, but are not limited to, fluorides, chlorides, bromides, and / or iodides. For ease of use and availability, the preferred halide is chloride. In order to improve activity, productivity and / or selectivity, the halide is the most preferred halide.

The halogen source may be any halogen-containing compound. Examples of such compounds include, but are not limited to, compounds of formula RmXn, wherein R may be any organic or inorganic radical, X may be a halogen selected from the group consisting of fluoride, chloride, bromide and / or iodide and am + n may be Any number greater than 0. When R is an organic radical, preferably R has from about 1 to about 70 carbon atoms per radical, more preferably 1 to 20 carbon atoms per radical, for its better compatibility and activity of the catalyst system. When R is an inorganic radical, R is preferably selected from the group consisting of aluminum, silicon, germanium, hydrogen, boron, lithium, tin, gallium, indium, lead and mixtures thereof. Specific examples include, but are not limited to, methylene chloride, chloroform, benzyl chloride, silicon tetrachloride, stannous chloride, tin tetrachloride, germanium chloride, boron trichloride, aluminum bromide, aluminum chloride, 1,4-dibromobutane and / or 1-bromobutane. .

Further, a chromium source, an alkyl metal and / or an unsaturated hydrocarbon may contain and provide a halide to the reaction mixture. Preferably the alkyl halide source is an alkyl aluminum halide and is used in conjunction with alkylaluminum compounds for ease of use and compatibility, as well as improving catalyst activity and product selectivity. Examples of alkylaluminium halides include, but are not limited to, diisobutylaluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, diethylaluminum iodide, and mixtures thereof.

If the desired product is a trimerization catalyst system, the reaction mixture preferably comprises a halide source. Most preferably, the halide source is selected from the group consisting of tin halides, germanium halides and mixtures thereof. The halide source is most preferably combined with a chromium source and a pyrrole-containing compound prior to the addition of the alkyl metal, i.e. a chromium source and

The pyrrole-containing compound is pretreated with a halide source to increase the productivity of the catalyst system.

The amount of each reactant used to prepare the trimerization catalyst system may be any amount that, when combined with one or more olefins, is sufficient to carry out the trimerization as defined herein. Typically, to prepare a trimerization catalyst system, about one mole of chromium, as a chromium (Cr) element, may be combined with about 1 to about 50 moles of pyrrole-containing compound and about 1 to about 75 moles of aluminum, as an element, in excess of unsaturated hydrocarbon. . If a halide source is optionally present, about 1 to about 75 moles of halide is generally present as the element. Preferably, about 1 mol of chromium, calculated as the chromium (Cr) element, may be combined with a 1 to about 15 mol of pyrrole-containing compound and about 5 to about 40 mol aluminum, calculated as the aluminum (Al) element, in excess of the unsaturated hydrocarbon. If a halide source is optionally present, preferably about 1 to about 30 moles of halide is present, calculated as elemental halogen (X). Most preferably, about one mole of chromium element (Cr) is combined with two to four moles of pyrrole-containing compound and 10 to 20 moles of aluminum element (Al) in excess of an unsaturated hydrocarbon. If a halide source is optionally present, most preferably 2 to 15 moles of halide are present as element (X).

Excess pyrrole-containing compounds do not exhibit an improvement in catalyst system activity, productivity and / or selectivity. The unsaturated hydrocarbon can improve the stability of the catalyst system, activity and / or selectivity. Excess unsaturated hydrocarbon can damage selectivity and / or activity of the catalyst system. Too much alkylaluminum reduces catalyst system activity and product selectivity. Too little alkylaluminum can lead to incomplete formation of the catalyst system, which can in turn lead to low catalyst system activity and increase the formation of undesirable polymer by-products. An excess of the optional halide source may deactivate the catalyst system and may thus lead to reduced activity of the catalyst system. As noted, the presence of a halide source may increase catalyst system activity and product selectivity.

According to a fourth aspect of the invention, preferably the pyrrole-containing compound is present in the reaction mixture together with the metal source prior to the introduction of the alkyl metal. When the addition is carried out in this order, a better catalyst system can be obtained in terms of product selectivity and activity and productivity of the catalyst system.

The reaction is preferably carried out in the absence of oxygen which can deactivate the catalyst and under anhydrous conditions, i.e., in the initial absence of water. Most preferred is a dry, inert atmosphere such as nitrogen and / or argon. Further, the alkyl metal is a non-hydrolyzed alkyl metal.

The reaction pressure may be any pressure that does not adversely affect the reaction. In general, pressures ranging from about atmospheric pressure to about 300 psig are acceptable. For ease of operation, atmospheric pressure is generally used.

The reaction temperature may be any temperature. For greater reaction efficiency, temperatures that keep the reaction mixture in a liquid state are preferred for the above reasons.

The reaction time may be any time required for the reaction to proceed. The reaction can be considered as a dissolution process; any time that substantially all of the reactants can dissolve is sufficient. Depending on the reactants as well as the reaction temperature and pressure, the reaction time may vary. Usually less than about 1 day may be sufficient. Typically, the reaction time is less than about 60 minutes. Under optimal conditions, the reaction time may range from about 1 second to about 15 minutes. A longer time usually does not provide further improvement and a shorter time may not be sufficient for a complete reaction.

-9EN 287405 B6

A heterogeneous, i.e., supported, catalyst system may be prepared in accordance with a fourth aspect of the invention in situ in a reactor by adding a solid support directly to the reactor. As noted, examples of catalyst supports include, but are not limited to, zeolites, inorganic oxides, either alone or in combination, phosphated inorganic oxides and mixtures thereof. Particularly preferred are carriers selected from the group consisting of silica, silica-alumina, alumina, fluorinated alumina, silated alumina, thorium oxide, aluminum phosphate, aluminum phosphate, phosphated silica, phosphated alumina, silica-titanium dioxide, co-precipitated silica / titanium dioxide, fluoridated / silated alumina and mixtures thereof, and preferably those wherein one or more of these carriers may contain chromium. The most preferred catalyst support is, for the greatest trimerization activity, aluminophosphate, as disclosed in U.S. Pat. No. 4,366,855. In situ preparation of a heterogeneous catalyst system used in a trimerization or oligomerization process can reduce unwanted polymer formation.

Heterogeneous trimerization, oligomerization and / or polymerization catalyst systems can also be prepared in accordance with this aspect of the invention by providing a reaction mixture comprising a chromium source, a pyrrole-containing compound, an alkyl metal, an unsaturated hydrocarbon and an inorganic oxide as mentioned above. Optionally, as mentioned, a halide source may be added. The reaction stoichiometry and reaction conditions are the same as those described in the second embodiment of the invention.

Any excess of the chromium source relative to the inorganic oxide catalyst support is sufficient. However, less than about 5 grams of chromium-pyrrolidide compound per gram of catalyst support is sufficient. Preferably, about 0.001 to about 0.01 to 0.5 grams of chromium-pyrrolidine compound, or chromium source, is used per gram of carrier, for best carrier loading and most efficient reagent utilization. The amount of chromium pyrrolides or chromium source, as a compound per gram of carrier, can be expressed in different ways, in equivalent terms such as mol of chromium per gram of carrier. Typically less than about 8.6 x 10 ^-3 moles of chromium per gram of carrier are sufficient. Preferably, about 1.7 x 10 ^-6 to about 1.7 x 10 ^-5 to 8.6 x 1 (Γ * mol of chromium per gram of carrier is used, for the above reasons).

The resulting heterogeneous catalyst system may be separated by filtration to yield a solid product-catalyst system. The solid catalyst system is preferably maintained under a dry, inert atmosphere to maintain chemical stability and reactivity.

EP-A-417477 discloses a polymerization catalyst and cocatalyst system, the cocatalyst comprising chromium compounds according to EP-A-416304. In general, polymerization catalyst systems are considered either as chromium-based catalysts (also known as "Phillips catalysts") or as catalysts containing titanium, zirconium and / or vanadium.

Any chromium catalyst system known in the art can be used. Commercially available chromium-based catalyst systems typically include chromium, at least a portion of which is in a festive state, based on an inorganic oxide; optionally, the polymerization catalyst system may further comprise an alkyl metal cocatalyst. Examples of chromium-based catalyst systems include, but are not limited to, those described in US 3887494, US 3900457, US 4053436, US 4151122, US 4294724, US 4392990 and US 4405501.

Any catalyst system containing titanium, zirconium and / or vanadium known in the art can also be used. A commercially available catalyst system comprising titanium, zirconium and / or vanadium typically comprises transition metal halide complexes with organometallic compounds. Examples of magnesium / titanium catalysts include, but are not limited to, those described in US 4394291, US 4326988 and US 4347158.

The amount of novel trimerization and / or oligomerization cocatalyst systems containing the chromium compounds of the invention used as cocatalyst may be any amount

Sufficient to form a comonomer that can be incorporated into the polymer product. The chromium-based catalyst systems prepared according to various aspects of the present invention can serve as cocatalysts in conjunction with the above-mentioned catalysts containing titanium, zirconium and / or vanadium.

The process of the aforementioned fourth aspect of the invention in combination with a metal source, a pyrrole containing compound and an alkyl metal and preferably an unsaturated hydrocarbon avoids the need to isolate the first reaction product, as in the processes described in the above-mentioned applications. Further, the catalyst system produced by the process of the fourth aspect of the invention has improved productivity and selectivity to the desired trimerization product, for example in the production of 1-hexene from ethylene.

Polymerization reactants

The reactants applicable for use in polymerization with the catalyst systems and cocatalyst systems and methods of the invention are olefinic compounds that can polymerize, i.e., react together or with other olefinic compounds. The catalyst systems of the invention can be used to polymerize at least one linear or branched mono-1-olefin having about 2 to about 8 carbon atoms. Examples of compounds include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof.

The catalyst systems of the present invention are also useful in oligomerization processes using olefinic compounds having from about 2 to about 30 carbon atoms and having at least one olefinic double bond. Examples of mono-olefinic compounds include, but are not limited to, acyclic and cyclic olefins such as ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3heptene, four normal octenes, four normal nonenes and mixtures of two or more of said compounds. Examples of diolefinic compounds include, but are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene and 1,5-hexadiene. If branched and / or cyclic olefins are used as reactants, regardless of theory, it is believed that steric hindrances could interfere with the trimerization process. Therefore, the branched and / or cyclic olefin portion (s) should preferably be distant from the carbon-carbon double bond.

Trimerization, as used herein, is defined as a combination of any two, three, or more olefins wherein the number of olefinic, i.e., double bonds, is reduced to two. The reactants useful in the trimerization process of the invention are olefinic compounds which can a) react themselves, i.e., trimerize, to produce suitable products such as, for example, reaction of ethylene alone can give 1-hexene and reaction of 1,3-butadiene alone can give 1.5 - cyclooctadiene and / or b) olefinic compounds which can react with other olefinic compounds, i.e. co-trimerize, to produce suitable products, such as co-trimerization of ethylene plus hexene, can provide 1-decene and / or 1-tetradecene, co- trimerization of ethylene and 1-butene provides 1-octene, co-trimerization of 1-decene and ethylene can provide 1-tetradecene and / or 1-docosene, or co-trimerization of 1,3-butadiene and 1,5-hexadiene can provide 1,5- cyclooktadekadien. For example, the number of olefinic bonds in a combination of three ethylene units is reduced by two, per olefinic bond, in 1-hexene. In another example, the number of olefinic bonds in the combination of two 1,3-butadiene units is reduced by two, to two olefinic bonds in 1,5-cyclooctadiene. As used herein, the term "trimerization" is intended to include dimerization of diolefins as well as "co-trimerization" as set forth above.

Suitable trimerizable olefinic compounds are those having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond. Examples of monoolefinic compounds include, but are not limited to, acyclic and cyclic olefins such as ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2hexene, 3-hexene, 1-butene. heptene, 2-heptene, 3-heptene, four normal octenes, four normal nonenes and mixtures of two or more of said compounds. Examples of diolefinic compounds include, but are not limited to

These are, but are not limited to, 1,3-butadiene, 1,4-pentadiene and 1,5-hexadiene. If branched and / or cyclic olefins are used as reactants, without being bound by theory, it is believed that steric hindrances could interfere with the trimerization process. Therefore, the branched and / or cyclic olefin fraction (s) should preferably be distant from the carbon-carbon double bond.

Catalyst systems produced in accordance with the present invention are preferably used as trimerization catalyst systems.

Reaction conditions

Reaction products, i.e. trimers and / or polymers, can be prepared from the catalyst systems of the invention by solution reactions, slurry reactions and / or gas phase reactions using conventional equipment and a contact process. Contact of the monomer or monomers with the catalyst system or with the polymerization catalyst system and the trimerization / oligomerization cocatalyst system can be accomplished by any method known in the art for homogeneous (liquid) or heterogeneous (solid) catalyst systems. One common method is to suspend the catalyst system in an organic medium and mix the mixture to keep the catalyst system in suspension during trimerization, oligomerization and / or polymerization. Other known contact methods such as fluidized bed, gravity bed and fixed bed may also be used. A common method with catalyst / cocatalyst systems is to suspend the polymerization catalyst system in an organic medium and mix the mixture to keep the polymerization catalyst system in suspension during the trimerization and / or polymerization process. A cocatalyst system according to the invention may be added. Advantageously, the polymerization catalyst system and the cocatalyst system of the invention may be simultaneously introduced into the polymerization reactor by one or more streams supplying the catalyst and / or cocatalyst system. Other contacting methods such as fluidized bed, gravity bed and fixed bed can also be used with all of these catalyst systems.

Reaction temperatures and pressures can be any temperatures and pressures that can trimerize, oligomerize and / or polymerize olefin reactants. Generally, reaction temperatures range from about 0 to about 250 ° C. Preferably, reaction temperatures in the range of about 60 to about 200 ° C and most preferably in the range of from 80 to 150 ° C are used. Generally, reaction pressures ranging from about atmospheric pressure to about 17.2 MPa are used. Preferred are reaction pressures in the range of about atmospheric pressure to about 7 MPa, and most preferably in the range of 2 to 5 MPa.

Too low reaction temperatures can produce too much undesirable insoluble product and too high temperatures can cause decomposition of the catalyst system and reaction products. Too low a reaction pressure can lead to low activity of the catalyst system. Too high a pressure can produce too much undesirable product.

Optionally, hydrogen may be added to the reactor to accelerate the reaction and / or increase the activity of the catalyst system.

The catalyst systems of the invention are particularly suitable for use in trimerization and / or oligomerization. The suspension process is usually carried out in an inert diluent (medium) such as paraffin, cycloparaffin or an aromatic hydrocarbon. Examples of diluents used in the reactor include, but are not limited to, isobutane and cyclohexane. Isobutane may reduce the swelling of the polymer product. The homogeneous trimerization and / or oligomerization cocatalyst system is more soluble in cyclohexane. Therefore, a preferred diluent for homogeneous trimerization or oligomerization is cyclohexane, and a preferred diluent for heterogeneous trimerization or oligomerization is isobutane. When the reactant is predominantly ethylene, a temperature in the range of about 0 to about 300 ° C, preferably in the range of about 60 to about 150 ° C is usually used.

Any amount of polymerization catalyst system and cocatalyst system can be present in the polymerization reactor to produce a polymer with the desired

A set of optimum properties, such as density, melt index, high load melt index, and molecular weight, are used. Preferably up to about 40 parts by weight of the supported, i.e. heterogeneous, cocatalyst system may be present for each part by weight of the polymerization catalyst system. Preferably, about 1 to about 25 parts of the cocatalyst system are present for each part of the polymerization catalyst system, and most preferably about 3 to 15 parts by weight of the cocatalyst system are present for each part of the polymerization catalyst system to produce a polymer with desired physical and processing characteristics.

Products

The olefinic and / or polymeric products of the invention have utility in a wide range of applications such as, for example, monomers for use in the preparation of homopolymers, copolymers and / or terpolymers. The polymeric products of the invention have applications in a wide range of applications such as polyethylene.

The invention will be explained in more detail and its advantages will be illustrated in the following examples.

DETAILED DESCRIPTION OF THE INVENTION

Various equivalent abbreviations are used throughout the description and examples. Some of them denote triethylaluminum as TEA, A1 (C ₂ H _{5) 3;} diethylaluminum chloride as DEAC, (A1 (C ₂ H _{5) 2,} C1); chromium (III) -2-ethylhexanoate such as Cr (EH) ₃ , CrEH, CrEH ₃ , hydrogen pyrrolidine such as pyrrole, Py, PyH, (C4H5N); chromium (III) acetonylacetonate such as Cr (acac) ₃ , Cracac ₃ , Cracac, Cr ( C ₅ H ₇ O _{2) 3,} chromium (III) pyrrolide as CrPy ₂ [Na (C 4 H ₁₀ 0 _{2) 2]} [Cr (C4H4N) ₃ Cl (C4Hio0 _2)], [Na (DME) _2] [Cr (C ₄ H ₄ N) ₃ Cl (DME)], [Na (DME) ₂ ] [Cr (Py) ₃ Cl (DME)], product V, compound V; chromium (III) tristetrahydrofuran as CrCl ₃ THF ₃ , CrCl ( THF) ₃ ; 2,5-dimethylpyrrole such as hydrogen-2,5-dimethylpyrrolidone, C ₆ H ₉ N, 2,5-DMP; butene as C ₄ =; 1-hexene as 1-C6 =; hexene as C ₆ =; octene as Cg =; decene as C] D =; dodecene as C] ₂ =; tetradecene as C] = _4.

Example I

Attempt 1001

0.14 g (0.29 mmol) chromium (III) -2-ethylhexanoate (CrEH) _3, [Cr (C _g Hi5O _{2) 3],} was weighed into a 25 mL pressure tube. The tube is sealed with a self-sealing crown cap, 0.062 ml (0.89 mmol) of pyrrole (PyH) [C ₄ NH ₅ ] and cyclohexane, as diluent to form the solution, are added via syringe in a total volume of about 8 ml.

0.9 ml of a 1.1 M solution (0.99 mmol) of triethylaluminum (TEA), [A1 (C ₂ H ₅ ) ₃ ] in heptane and a 0.9 ml portion of CrEH ₃ / PyH solution are added under countercurrent ethylene (quality) CP grade) into a 1 liter autoclave reactor containing 300 ml cyclohexane to form a catalyst system. The reactor is sealed and ethylene addition is terminated until the reactor temperature reaches a reaction temperature of 80 ° C. The ethylene pressure is increased to a total reactor pressure of 3.8 MPa. Ethylene is then fed as needed for 30 minutes. At the end of the experiment, a sample of the reaction mixture is taken and analyzed by capillary gas chromatography. The remaining reaction mixture was evaporated and the amount of solid product determined. The results are summarized in Table XXIII.

Attempt 1002

Experiment 1001 except that 8 mL of a 1.1 M solution (8.0 mmol) of TEA in heptane was added directly to the CrEH ₃ / PyH solution to form a solution (10 mL of total volume) and not to the reactor. A 0.7 ml aliquot of CrEH ₃ / PyH / TEA solution was added to the autoclave reactor. No additional TEA is introduced into the reactor. The results are summarized in Table XXIII.

-13GB 287405 B6

Attempt 1003

Experiment 1002 except that CrEH _{3 is} replaced with 0.10 g (0.29 mmol) of chromium (III) acetylacetonate (Cracac ₃ ), (Cr (C ₅ H ₇ O 2) ₃ ) and for Cracac solution formation. ₃ / PyH / TEA (8 mL total volume) was used with 6 mL of a 1.1 M solution of TEA (6.6 mmol) in heptane. A 1.4 ml portion of Cracac ₃ / PyH / TEA solution was added to the autoclave reactor. The results are summarized in Table XXIII below.

Attempt 1004

Follow Experiment 1001, except that 0.9 ml of a 1 M solution (0.9 mmol) of diethylaluminum chloride (DEAC), (AlCl ₂ (C ₂ H ₅ ) ₂ ), in hexane was added to the CrEH ₃ / PyH solution to form CrEH ₃ / PyH / DEAC solution. A 0.65 ml aliquot of CrEH ₃ / PyH / DEAC solution and 0.9 ml of a 1.1 M solution (0.99 mmol) of TEA in heptane was added to the autoclave reactor. The results are summarized in Table XXIII.

Attempt 1005

Experiment 1001 except that 0.9 ml of a 1 M solution (0.9 mmol) of DEAC in hexanes was added to the CrEH ₃ / PyH solution and the resulting CrEH ₃ / PyH / DEAC solution was aged for 1 day at ambient temperature and pressure. under dry nitrogen. A 0.65 mL portion of an old CrEH ₃ / PyH / DEAC solution + 0.9 mL of a 1.1 M solution (0.99 mmol) of TEA in heptane was added to the autoclave reactor. The results are summarized in Table XXIII below.

Attempt 1006

Test 1001 was followed except that a solution was prepared using 0.13 ml of pyrrole. Next, 1.0 mL of a 0.1 M solution (0.1 mmol) of DEAC in hexanes was added to the reactor along with TEA. Use a 0.9 ml aliquot of CrEH ₃ / PyH solution. The results are summarized in Table XXIII below.

Attempt 1007

Experiment 1003 was followed except that 3 ml of a 1.9 M solution (5.7 ml) of TEA in toluene was used and toluene was substituted for the cyclohexane diluent to form a CrEH ₃ / PyH / TEA solution. Thus, an excess of toluene is present in the reactor. Use a 0.9 ml aliquot of CrEH ₃ / PyH / TEA solution. The results are summarized in Table XXIII below.

Attempt 1008

Experiment 1002 except that CrEH _{3 is} replaced by 0.10 g of chromium (1H) pyrrolidide (CrPy ₃ ), Cr (C ₄ H ₄ N) ₃ ClNa (C ₄ H ₁₀ O ₂ ) ₃ / (0.17 mmol) and prepare a solution using 0.04 mL (0.52 mmol) of PyH and 3.5 mL of 1.1 M TEA (3.85 mmol) in heptanes. The final volume of the solution was about 5 ml. A 1.0 ml aliquot of CrPy ₃ / PyH / TEA solution was used. The results are summarized in Table XXIII below.

Attempt 1009

The procedure of Experiment 1008 was followed except that 1.8 ml of a 1.9 M TEA solution (3.42 mmol) in toluene was used and toluene was replaced by cyclohexane in the preparation of CrPy ₃ / PyH / TEA solution. Thus, an excess of toluene is present in the reactor. A 1.4 ml aliquot of CrPy ₃ / PyH / TEA solution was used. The results are summarized in Table XXIII.

-14GB 287405 B6

Attempt 1010

Run 1008 except that no pure PyH was added during the preparation of the CrPy ₃ / TEA solution. A 1.4 ml aliquot of a solution of CrPy ₃ / TEA in cyclohexane was used. The results are summarized in Table XXIII below.

Attempt 1011

Experiment 1009 was followed except that no pure PyH was added during the preparation of the CrPy ₃ / TEA solution. A 1.4 ml aliquot of a solution of CrPy ₃ / TEA in toluene was used. Thus, excess toluene was present in the reactor. The results are summarized in Table XXIII.

Table XXIII

Homogeneous catalyst system

Pok. mgCr (element.) charge Activity (g product / gCr / h yield product tot. G wt. % by weight solid % liquid product distribution percent c ₄ = 1- _C6 = ^C 6 = c ₈ = C | ₀ - C12 " C | ₄ - 1001 1.6 11,000 8.8 94 6 2 89 ^a 2 6 <1 <1 1002 0.96 8,800 4.2 88 12 1 87 5 2 4 <1 <1 1003 2.6 9,800 12.8 64 36 2 81 4 4 5 1 1 1004 1.1 15,000 8.5 98 2 <1 - 92 " 1 6 <1 <1 1005 1.1 26,000 14.9 98 2 <1 88 4 6 <1 <1 <1 1006 1.5 12,000 9.0 98 2 <1 - 97 " 1 2 <1 <1 1007 2.6 3,500 4.6 50 50 2 86 4 3 3 <1 <1 1008 2.5 8,300 10.5 > 99 <1 1 83 5 <1 8 <1 1 1009 2.5 4,100 5.2 99 1 1 88 4 1 6 <1 <1 1010 2.5 7,100 8.9 97 3 <1 82 6 1 8 <1 1 1011 2.5 3,300 4.2 98 2 <1 89 4 1 5 <1 <1

^and Hexenes in total

Example II

It should be noted that the results in Table XXIII of Example X and the results in Table XXIV of Example XI are not directly comparable because the reactions were carried out in different reactors, under different conditions, using different feeds of ethylene and cyclohexane as well as different diluents. However, direct comparisons can be made in each example.

Pokus 2001

0.30 g (0.62 mmol) of chromium (III) -2-ethylhexanoate (CrEH ₃ ) (10.15 wt% Cr) was combined with 0.12 ml (1.73 mmol) of pure pyrrole (PyH) in 10 ml toluene. 2.8 ml of a 1.9 M triethylaluminum (TEA) solution (5.32 mmol) in toluene was added and the CrEH ₃ / PyH / TEA solution was stirred for 30 minutes under dry nitrogen at ambient temperature and pressure. The dark brown CrEH ₃ / PyH / TEA solution was filtered and excess toluene was removed by vacuum distillation to give 1.0 mL of a dark brown oil used as a catalyst system. In countercurrent ethylene, 0.5 ml (0.15 g CrEH ₃ ; 15.2 mg Cr) catalyst system and 4.0 ml nonane (internal reactor standard) are added to a 1 liter autoclave reactor at 80 ° C containing 1.2 liters. cyclohexane. The reactor is then pressurized to 40 bar with ethylene and the reaction is allowed to proceed for 30 minutes, adding ethylene as necessary.

The results are summarized in Table XXIV below.

-15GB 287405 B6

Pokus 2002

Experiment 2001 was followed except that diethylaluminum chloride was added in addition to the CrEH ₃ / PyH / TEA solution.

0.53 g (1.10 mmol) CrEH ₃ (10.15 wt% Cr) was combined with 0.52 mL (7.5 mmol) of pure PyH in 15 mL of toluene and stirred for 5 min. 9.0 mL of a 1.9 M TEA solution (17.1 mmol) in toluene was added and the CrEH ₃ / PyH / TEA solution was stirred overnight under nitrogen at ambient pressure and temperature. Excess toluene was removed from the resulting dark brown solution by vacuum distillation to give 2.5 ml of dark brown oil. 0.5 mL (10.8 mg, 0.21 mmol Cr) of a dark brown oil was combined with 1.0 mL 0.87 M (0.87 mmol) diethylaluminum chloride (DEAC) solution in nonane and CrEH ₃ (PyH) solution. The TEA / DEA was stirred overnight under dry nitrogen at ambient temperature and pressure. The resulting product is used as a catalyst system. In an ethylene countercurrent, 1.3 ml (9.4 mg Cr, 0.18 mmol Cr) of the catalyst system and 4.0 ml nonane (internal reactor standard) were placed directly in a 21 liter reactor at 80 ° C containing 1.2 liters of cyclohexane . The reactor is then pressurized with ethylene to 100 psi and the reaction proceeds for 30 minutes, ethylene being fed as needed.

The results are summarized in Table XXIV below.

Pokus 2003

0.33 mg (0.68 mmol) CrEH ₃ (10.15 wt% Cr) was combined with 0.13 mL (1.87 mmol) pure PyH in 10 mL toluene and stirred for 5 min. 1.9 mL of a 1 M (1.9 mmol) solution of DEAC in hexanes was added and the CrEH ₃ / PyH / DEAC solution was stirred under dry nitrogen at ambient temperature and pressure for 30 minutes to give a light yellow-green solution. 5.1 ml of a 1.9 M (9.7 mmol) solution of diethylaluminum chloride (DEAC) in toluene was added and the CrEH ₃ / PyH / DEAC / TEA solution was stirred for 0.5 h to give a dark yellow-brown solution. Excess toluene and hexane were removed from the dark yellow-brown CrEH ₃ / PyH / DEAC / TEA solution by vacuum distillation to leave a dark yellow-brown solution. The tan solution was dissolved and the total volume was adjusted to 25 mL in cyclohexane and used as a catalyst system (1.32 mg Cr / mL). In an ethylene countercurrent, 7.0 ml (9.2 mg Cr, 0.178 mmol Cr) of the catalyst system and 4.0 ml nonane (internal reactor standard) were fed directly into a 21 liter reactor at 80 ° C containing 1.2 liters of cyclohexane. The reactor was then pressurized to 50 psi with ethylene and the reaction was allowed to proceed for 30 minutes while adding ethylene as needed.

The results are summarized in Table XXIV.

Attempt 2004

Experiment 2002 was followed except that the CrEH ₃ / PyH / DEAC solution was diluted with cyclohexane before being charged to the reactor and hydrogen gas (H ₂ ) (0.34 MPa) was added to the reactor before pressurizing with ethylene.

0.30 g (0.62 mmol) of CrEH ₃ (10.15% Cr) was combined with 0.12 mL (1.73 mmol) of pure PyH in 10 mL of toluene. 1.7 mL of IM (1.7 mmol) DEAC solution in hexanes was added and the CrEH ₃ / PyH / DEAC solution was stirred for 5 minutes under dry nitrogen at ambient temperature and pressure. 1.8 ml of a 1.9 M (3.42 mmol) TEA solution in toluene was added and the CrEH ₃ / PyH / DEAC / TEA solution was stirred under dry nitrogen at ambient temperature and pressure for 30 minutes. The resulting dark brown solution was filtered and excess toluene and hexanes were removed by vacuum distillation to give 0.8 mL of a dark tan oil which was used as the catalyst system. In an ethylene countercurrent, 0.4 ml (15.2 mg Cr, 0.29 mmol Cr) of the catalyst system and 4.0 ml of nonane (internal reactor standard) are fed directly into a 21 liter reactor at 80 ° C containing 1.2 liters of cyclohexane . Into a reactor were introduced 0.34 bar of hydrogen (H _2), then pressurized with ethylene to 3.8 MPa. The reaction is carried out for 30 minutes with ethylene added as necessary.

-16GB 287405 B6

The results are summarized in Table XXIV below.

Pokus 2005

In a 500 mL Schlenk flask, 1.98 g (3.4 mmol) of CrPy ₃ (11.1 wt% Cr) was combined with 40 mL of toluene and 54 mL of a 1.9 M (102.6 mmol) TEA solution in toluene. The resulting dark brown reaction mixture was stirred for 1 hour under dry nitrogen at ambient temperature and pressure. Excess toluene was removed by vacuum distillation to give 13 ml of dark tan oil and a small amount of light colored precipitate. The dark yellow-brown oil is separated, removed from the precipitate by syringe and used as a catalyst system. 2.0 ml of the catalyst system was diluted with 27 ml of cyclohexane and aged for 3 days at ambient temperature and pressure under dry nitrogen before use.

Under countercurrent ethylene, 8.0 ml (9.3 mg, 0.18 mmol Cr) of the catalyst system / cyclohexane solution and 4.0 ml of nonane (internal reactor standard) are placed directly in a 21 liter autoclave reactor at 80 ° C containing 1, 2 liters of cyclohexane. The reactor is then pressurized with ethylene to 50 psi and the reaction is allowed to proceed for 30 minutes, ethylene being introduced as needed.

The results are summarized in Table XXIV below.

Pokus 2006

Experiment 2005 was followed except that less reactants were used and aging was not so long.

In a 500 mL Schlenk flask, 0.25 g (0.432 mmol) CrPy ₃ (11.1 wt% Cr) was combined with 10 mL toluene and 3.4 mL 1.9 mL (6.46 mmol) TEA solution in toluene. The resulting dark brown reaction mixture was stirred for 30 min under dry nitrogen at room temperature and ambient pressure. Excess toluene was removed by vacuum distillation to give a dark brown oil. All dark brown oil was diluted to a total volume of 25 mL with cyclohexane to give a solution containing 1.11 mg Cr / mL, which was used as the catalyst system.

With ethylene countercurrent, 8.0 ml (8.88 mg, 0.171 mmol Cr) of the catalyst system / cyclohexane solution and 4 ml of nonane (internal reactor standard) were fed directly into a 21 liter autoclave reactor at 80 ° C containing 1.2 liters of cyclohexane. The reactor was then pressurized to 50 psi with ethylene and the reaction was continued for 30 minutes while ethylene was introduced as needed.

The results are summarized in Table XXIV below.

Pokus 2007

Experiment 2005 was followed except that an excess of toluene was present in the trimerization reactor.

In a 500 ml Schlenk flask, 1.98 g (3.4 mmol CrPy ₃ (11.1 wt% Cr)) were combined with 40 mL toluene and 54 mL 1.9 M (102.6 mmol) TEA solution in toluene. The reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 1 hour, and excess toluene was removed by vacuum distillation to give 13 ml of dark tan oil and a small amount of pale colored precipitate. 2.0 ml of the catalyst system was diluted with 27 ml of cyclohexane and aged for 3 days under dry nitrogen at ambient temperature and pressure before use.

In an ethylene countercurrent, 0.5 ml (8.5 mg, 0.163 mmol Cr) catalyst system / cyclohexane, 4.5 ml toluene and 4.0 ml nonane (internal reactor standard) are fed directly into the 21 liter

The autoclave reactor at 80 ° C containing 1.2 liters of cyclohexane was used. The reactor is then pressurized with ethylene to 50 psi and the reaction proceeds for 30 minutes with ethylene feed as needed.

The results are summarized in Table XXIV below.

Pokus 2008

Cracac ₃ (0.28 g, 0.802 mmol) was combined with pure pyrrole (0.17 mL, 2.45 mmol) in toluene (10 mL) and stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. 6.3 ml of a 1.9 M (12.0 mmol) TEA solution in toluene are then added. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 30 minutes. The excess toluene was removed by vacuum distillation to give a dark tan oil. All dark tan oil was diluted to 25 mL with cyclohexane to give a solution containing 0.0112 g Cracac ₃ / mL, which was used as the catalyst system.

In an ethylene countercurrent, 7.0 ml (15.2 ml, 0.293 mmol Cr) of the catalyst system / cyclohexane solution and 4.0 ml of nonane (internal reactor standard) were fed directly into a 21 liter autoclave reactor at 80 ° C containing 1.2 liters. cyclohexane. The reactor was then pressurized to 50 psi with ethylene and the reaction was continued for 30 minutes while adding ethylene as needed.

The results are summarized in Table XXIV.

Pokus 2009

Experiment 2008 was followed except that chromium (III) naphthenate was used as the chromium source.

0.33 g (0.508 mmol) of CrNapth ₃ (8.0 wt% Cr) was combined with 0.12 mL (1.73 mmol) of pure pyrrole in 10 mL of toluene and stirred under dry nitrogen at ambient temperature and pressure 5. minutes. 4.6 ml of a 1.9 M (8.74 mmol) TEA solution in toluene are then added. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 30 minutes. Excess toluene was stripped off in vacuo to give a dark tan oil. All dark tan oil was diluted to a total volume of 25 mL with cyclohexane to give a solution containing 1.066 mg Cr / mL, which was used as the catalyst system.

In countercurrent ethylene, 7.0 ml (7.39 mg, 0.142 mmol Cr) of catalyst system / cyclohexane solution and 4.0 ml of nonane (internal reactor standard) are placed directly in a 21 liter autoclave reactor at 80 ° C containing 1.2 liters. cyclohexane. The reactor was then pressurized with ethylene to 100 psi and the reaction was allowed to proceed for 30 minutes, ethylene being introduced as needed.

The results are summarized in Table XXIV below.

Pokus 2010

Experiment 2008 was followed except that chromium chloride was the source of chromium.

0.41 g (1.09 mmol) of CrCl ₃ THF ₃ was combined with 0.23 ml (3.32 mmol) of pure pyrrole in 10 ml of toluene and stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Then 8.6 ml of a 1.9 M (16.3 mmol) TEA solution in toluene are added. The resulting dark brown reaction mixture was stirred for 30 minutes under dry nitrogen at ambient temperature and pressure. Excess toluene was removed by removal in vacuo to give a dark tan oil. 7.5 ml of nonane are added to this dark yellow oil and the resulting solution is diluted to a total volume of 25 ml with cyclohexane to give a solution containing 0.0164 g of CrCl ₃ THF ₃ / ml. The solution was filtered and the filtrate was used as the catalyst system.

-18GB 287405 B6

In an ethylene countercurrent, 5.0 ml (11.38 mg, 0.219 mmol Cr) of the catalyst system / cyclohexane / nonane solution and 2.5 ml of nonane (internal reactor standard) were fed directly into a 21 liter autoclave reactor at 80 ° C containing 1 , 2 liters of cyclohexane. The reactor was then pressurized to 50 psi with ethylene and the reaction was continued for 30 minutes with ethylene introduced as needed.

The results are summarized in Table XXIV below.

Attempt 2011

Experiment 2005 was followed except that excess hexene was placed in the trimerization reactor.

In a 500 mL Schlenk flask, 1.98 g (3.4 mmol) of CrPy ₃ (11.1 wt% Cr) was combined with 40 mL of toluene and 54 mL of a 1.9 M (102.6 mmol) TEA solution in toluene. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 1 hour. Excess toluene was removed by removal in vacuo to give 13 ml of a dark tan oil and a small amount of a light colored precipitate. The dark yellow-brown oil is separated, the precipitate is removed by syringe and used as a catalyst system. 2.0 ml of the catalyst system were diluted with 27 ml of cyclohexane and aged for 3 days under dry nitrogen at ambient temperature and pressure before use.

In countercurrent ethylene, 1.0 mL (16.9 mg, 0.325 mmol Cr) of catalyst system / cyclohexane solution, 55 mL of 1-hexene and 4.0 mL of nonane (internal reactor standard) was placed directly in a 21 liter autoclave reactor at 80 ° C. containing 1.2 liters of cyclohexane. The reactor was then pressurized to 50 psi with ethylene and the reaction was continued for 30 minutes with ethylene introduced as needed.

The results are summarized in Table XXIV below.

Attempt 2012

Experiment 2005 was followed except that the chromium source was chromium (II) pyrrolidine (compound I).

0.30 g (about 0.85 mmol) of compound I (CrPy1 _O THF ₄ ) was combined with 10 mL of toluene and 6.7 mL of a 1.0 M (12.7 mmol) TEA solution in toluene. The resulting dark brown reaction mixture was stirred for 30 minutes under dry nitrogen at ambient temperature and pressure. Excess toluene was removed by removal in vacuo to give a dark tan oil and a small amount of a light colored precipitate. Dark yellow-brown oil was filtered and the filtrate was diluted to a total volume of 25 ml with cyclohexane to give a solution containing 0.012 g Compound I ₍₀ CrPyi THF _4), used as catalyst system.

In countercurrent ethylene, 7.0 ml of the catalyst system / cyclohexane solution and 4.0 ml of nonane (internal reactor standard) were placed directly in a 21 liter autoclave reactor at 80 ° C containing 1.2 liters of cyclohexane. The reactor was then pressurized to 50 psi with ethylene and the reaction was continued for 30 minutes with ethylene introduced as needed.

The results are summarized in Table XXIV below.

-19GB 287405 B6

Table XXIV

Catalyst system with solvent removal

Pok. mgCr (element) charge molar ratio Cr: Py: TEA: DEAC Activity (g product / gCr / h) total product yield, g % wt. wt. % fixed % liquid product distribution% wt. C ₄ = 1-C6 = C ₆ = c, = C10 " C12 C | 4 " 2001 15.2 1: 3: 9: 0 4,000 30.5 74 26 9 53 2 9 9 5 4 2002 9.3 1: 7: 15.5: 3 6,000 23.2 95 5 <1 88 4 2 3 <1 <1 2003 9.2 1: 3: 15: 3 8,300 38.5 88 12 <1 86 3 2 5 <1 <1 2004 15.2 1: 3: 6: 3 4,900 37.0 96 4 <1 91 2 2 3 <1 <1 2005 7.5 1: 3: 30: 0 10,600 40.0 98 2 <1 82 9 1 7 <1 <1 2006 7.2 1: 3: 15: 0 10,800 38.9 97 3 <1 81 5 3 7 <1 1 2007 6.8 1: 3: 30: 0 1,100 3.2 94 6 4 84 6 1 4 <1 <1 2008 11.8 1: 3: 15: 0 17,000 98.9 95 5 <1 84 5 1 6 <1 <1 2009 7.4 1: 3: 15: 0 15,700 57.8 72 28 <1 88 2 2 5 <1 <1 2010 11.4 1: 3: 15: 0 8,000 45.3 98 2 <1 88 4 1 5 <1 <1 2011 13.7 1: 30: 0: 0 4,600 31.3 - - <1 76 11 1 10 <1 2012 10.0 1: 2: 18.5: 0 8,800 44.1 99 1 <1 77 9 1 11 <1 1

Example III

Attempt 3001

Cracac ₃ (0.21 g, 0.601 mmol) was combined with pure pyrrole (0.12 mL, 1.73 mmol) and toluene (15 mL). The resulting solution was stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Then 6.0 ml of a 1.9 Μ (11.4 mmol) TEA solution in toluene is added. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Then, 2 g of an aluminophosphate carrier (0.4 P / Al molar ratio, activated at 700 ° C), prepared according to U.S. Pat. No. 4364855 (1982), herein incorporated by reference, is added, and the resulting suspension is stirred for about 12 hours. The product was collected by filtration, washed at least twice with 10 ml portions of toluene and pentane until no color was observed in the filtrate and dried under vacuum. The dried product is used as a supported supported catalyst system.

A 2.1022 g portion of the solid catalyst system was added in countercurrent ethylene to a 21 liter autoclave containing 1 liter of isobutane. Before the catalyst is introduced, 0.25 ml of 16.5 wt. TEA of a non-vane solution to neutralize any poisons for the ethylene feedstock that might be present. The reactor is sealed and ethylene addition is terminated until the temperature of the reactor reaches the temperature required for the experiment, for example 90 ° C. The ethylene pressure was then increased to a total reactor pressure of 3.8 MPa. Ethylene is introduced as necessary over the 30 minute duration of the experiment. At the end of the experiment, a sample of the liquid reaction mixture is taken and analyzed by gas chromatography. The remaining reaction mixture was evaporated and the amount of solid product determined.

The results are summarized in Table XXV.

Attempt 3002

Experiment 3001 was followed except that diethylaluminum chloride was added to the Cracac ₃ / PyH solution together with TEA prior to the addition of the aluminophosphate inorganic oxide.

Weigh 0.21 g of Cracac ₃ (0.60 mmol) into a 30 ml screw cap vial. 0.12 ml of PyH (1.73 mmol) and 15 ml of toluene were added and the resulting solution was sealed and stirred for 5 minutes. 6 ml of a 1.9 Μ (11.4 mmol) TEA solution in toluene are then added with continued stirring. After stirring the Cracac ₃ / PyH / TEA solution for 5 minutes, 2.4 ml of a 1M (2.4 mmol) DEAC solution in hexanes was added and the Cracacs / PyH / TEA / DEAC / toluene solution was stirred for 5 minutes. 2.0 g of an aluminophosphate carrier (0.4 P / Al molar ratio, activated at 700 ° C), prepared according to US 4364855 (1982), cited herein by reference, are added and the resulting suspension is stirred for about 12 hours. The product is

287405 B6 was collected by filtration and washed at least twice with 10 ml portions of toluene and pentane until no color was observed in the filtrate and dried under vacuum. The dried product is used as a solid, supported catalyst system.

A 0.5048 g portion of the solid catalyst system was added countercurrently to ethylene to a 21 liter autoclave reactor containing 1 liter of isobutane. 3.0 ml of 1.6 wt. TEA of a non-vane solution to neutralize any poisons of the ethylene feedstock that may be present. The reactor is closed and the addition of ethylene is terminated when the temperature in the reactor reaches the temperature required for the experiment, for example 90 ° C. The ethylene pressure is increased to a total reactor pressure of 3.8 MPa. Ethylene is then introduced as needed after 30 minutes of experiment. At the end of the experiment, a small sample of the liquid reaction product mixture is taken and analyzed by piano chromatography. The remaining reaction mixture was evaporated and the amount of solid product determined. The ethylene consumption is determined by a calibrated flowmeter.

The results are summarized in Table XXV below.

Attempt 3003

Experiment 3002 was followed except that the source of chromium was CrEH ₃ and no aromatic solvent was used during the preparation of the catalyst system. The catalyst system is also prepared in situ in the reactor.

A CrEH ₃ / PyH solution is prepared by mixing 0.33 g (0.69 mmol) of CrEH ₃ with 0.26 ml (3.75 mmol) of PyH in 16 ml of pentane and aged for 4 days under nitrogen at room temperature and pressure. environment before use. 0.49 g aluminophosphate carrier (0.9 P / Al molar ratio, activated at 700 ° C), prepared according to US 4364855 (1982), cited herein by reference, and 2.0 mL of 1M (2.0 mmol) TEA solution in hexane are placed in countercurrent ethylene in a 21 liter autoclave reactor at room temperature. Then, 1 liter of cyclohexane, 2.1 ml (4.32 mg, 0.083 mmol Cr) of CrEH ₃ / PyH solution was charged to the reactor and 0.34 MPa of hydrogen (H ₂ ) was introduced into the reactor.

The results are summarized in Table XXV below.

Table XXV

Try vsádka kat.syst. grams molar ratio Cr: Py: TEA: DEAC activity (g prod / g cat./h) product total yield. G wt. % wt. % liquid product distribution % c ₄ = 1-Cn = C ₆ = Cs = Cio ^- C12 ^- C14 ” 3001 2.1022 - 210 223 82 18 1 76 7 2 11 1 2 3002 0.5048 1: 3: 19: 4 340 87 99 1 1 82 7 1 8 <1 1 3003 0,0426 ' 1: 5.5: 22.6: 0 450 224 88 12 6 61 6 5 13 2 3

If only g Cr (EH) _{3 is used} , the presence of other components of the catalyst system is excluded

Example IV

Experiment 4001

Weigh 3.5 g (10 mmol) of Cracac ₃ into a 100 ml pressure tube. The mixing rod is placed in the tube and the tube is closed with a self-sealing crown cap. 40 ml of toluene and 2.1 ml (30 mmol) of PyH are added via syringe. 12 ml of a 2.5 M (30.0 mmol) solution of n-butyllithium in hexanes is slowly added. A precipitate formed, separated and washed with one 10 ml portion of toluene and two 10 ml portions of cyclohexane until no color was observed in the wash solution. A total of 5.59 g of solid is obtained. Use 0.5 ml of a 1.1 M (0.55 mmol) TEA solution in heptane and a suspension of 38 mg of solid and cyclohexane in the reaction described in Experiment 1001.

-21EN 287405 B6

The results are summarized in Table XXVI below.

Experiment 4002

Experiment 4001 except that the solid catalyst component (88 mg collected) was prepared in a 25 mL pressure tube using 0.349 g (1 mmol) Cracac ₃ , 5 mL toluene, 0.14 mL (2 mmol) PyH and 0. 1.8 ml of a 2.5M (2.0 mmol) solution of n-butyllithium in hexane.

0.5 ml of a 1.1 M (0.55 mmol) TEA solution in heptanes and a suspension in cyclohexane containing 16 mg of solid are used in the reaction under the conditions described in Example 1001.

The results are summarized in Table XXVI below.

Experiment 4003

1.0 g of an aluminophosphate carrier (0.4 P / Al molar ratio, activated at 700 ° C), prepared according to U.S. Patent 4364855 (1982), which is incorporated herein by reference, and 93 mg solids content described in Experiment 4001, weigh into a 25 ml pressure tube. The pipe is closed. 5 ml of toluene and 3 ml of a 1.9 M (5.7 mmol) TEA solution in toluene are added via syringe. The resulting suspension was stirred for one day. The solid was isolated and washed with 10 ml portions of toluene and cyclohexane until the color in the wash solutions had disappeared.

Use 0.5 ml of a 1.1 M (0.55 mmol) TEA solution in heptanes and a cyclohexane suspension containing 80 mg of solid in the reaction under the conditions described in Experiment 1001.

The results are summarized in Table XXVI below.

Experiment 4004

0.7 g of aluminophosphate carrier (0.4 P / Al molar ratio, activated at 700 ° C), prepared according to US 4364855 (1982) herein incorporated by reference, and a portion (53 mg) of the solid described in Experiment 4002 are weighed. into a 25 ml pressure tube. The pipe is closed. 3.5 ml of toluene and 2 ml of a 1.9 M (3.8 mmol) TEA solution in toluene are added to the tube by syringe. The resulting suspension was stirred for one day. The solid was collected and washed with 10 ml portions of toluene and cyclohexane until no color of the wash solution was observed.

0.5 ml of a 1.1 M (0.55 mmol) TEA solution in heptane and a cyclohexane suspension containing 78 mg of solid are used in the reaction under the conditions described in Experiment 1001.

The results are summarized in Table XXVI below.

Table XXVI

Alkyllithium in catalyst preparation

Try gramy katal. inserts activity / g prod./g cat./h / product total yield G % wt. likvid. % wt. solid distribution of liquid products c ₄ = 1 — What? c ₆ = C ₈ = Customs ^- C12 " Cu ” 4001 0,038 95 1,8 86 14 4 81 5 3 4 <1 <1 4002 0.016 540 4.3 82 18 3 83 5 3 4 <1 <1 4003 0,080 110 4.3 89 11 1 79 5 3 5 2 1 4004 0,078 310 12.2 84 16 1 78 6 2 8 1 1

-22EN 287405 B6

Example V

Attempt 5001

Weigh 0.17 g of chromium (III) -2,2,6,6-tetramethyl-3,5-heptanedionate (Cr (III) TMHD) (0.28 mmol) into a 25 ml pressure tube. The tube is closed with a self-sealing crown cap. 0.06 ml of pyrrole (0.89 mmol) and 0.17 ml of pure (0.87 mmol) diisobutylaluminum chloride (DiBAlCl) are added via syringe to form a Cr (III) TMHD / DiBAlCl / Py solution which is diluted to a total volume of about 8 ml of cyclohexane. 0.25 ml of 1.1 M (0.28 mmol) TEA solution in heptane and 0.75 ml solution

Cr (III) TMHD / DiBAlCl / Py is added to a glass container containing 100 ml cyclohexane and 10 g butadiene. The glass vessel was placed in a 70 ° C bath at ambient pressure and stirred for 16 hours. After 16 hours a small sample of the liquid reaction product mixture is taken and analyzed by gas chromatography. The residual liquid reaction product was evaporated and the amount of solid product was determined.

The results are summarized in Table XXVII below.

Attempt 5002

Experiment 5001 was followed except that no excess alkylaluminum compound was present in the reactor and the catalyst was obtained as described in Experiment 3001.

Cracac ₃ (0.21 g, 0.601 mmol) was combined with pure pyrrole (0.12 mL, 1.73 mmol) and toluene (15 mL). The resulting solution was stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Then 6.0 ml of a 1.9 Μ (11.4 mmol) TEA solution in toluene is added. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. 2.0 g of an aluminophosphate carrier (P / Al molar ratio of 0.4 activated at 700 ° C), prepared according to US 4364855 (1982), which is incorporated herein by reference, are then added and the resulting suspension is stirred for 30 hours. about 12 hours. The product is filtered off, washed with at least twice 10 ml portions of toluene and pentane until the filtrate is colorless and dried under vacuum. The dried product is used as a solid, supported catalyst system.

In the butanedien reaction, 0.28 g of the catalyst batch was used.

The results are summarized in Table XXVII below.

Table XXVII

Reactions of butadiene

Try % conversion of butadiene to product product distribution, wt. % 1,5-cyclooctadiene other liqu. fixed 1. 5001 97 91.9 0.3 7.8 5002 68 60.8 2.5 36.7

Example VI

In the following experiments, all catalysts were prepared in a glovebox, under dry nitrogen at ambient temperature and pressure. The transition metal compounds were weighed and combined with three (3) equivalents (0.062) ml of pyrrole, 2 ml of cyclohexane as solvent and 6 ml of a 1.1 M solution of triethylaluminum (TEA) in heptane. The resulting product is shaken for a time ranging from 5 minutes to 50 hours.

-23GB 287405 B6

All experiments were carried out in a 1 liter autoclave reactor containing 300 ml of cyclohexane. 1.0 ml of the liquid catalyst system was diluted in cyclohexane and added to the reactor under countercurrent ethylene (step CP). The reactor is sealed and ethylene addition is terminated when the reactor temperature reaches a reaction temperature of 80 ° C. The ethylene pressure is increased to a total reactor pressure of 3.8 MPa. Ethylene is supplied as needed for 30 minutes in the experiment. If necessary, a heater is applied to maintain the reactor temperature at 80 ° C.

At the end of each experiment, a sample of the liquid reaction product mixture was sampled and analyzed by capillary gas chromatography on an HP-5880 gas chromatography equipped with a FID detector and a 60-meter DB-1 column with an internal diameter of 0.25 mm and 0.25 µm film. The gas chromatograph was programmed from 40-275 ° C at 10 ° C min ^_1 for 20 minutes residence time. Cyclohexane was used as internal standard. The remaining reaction product was evaporated and the amount of solid product determined.

The results are shown in Table XXVIII.

Table XXVIII

Try metal. col. grams metal. look cat. grams cat. activity (g prod./ and cat./h) gramy tot. prod. wt. % liqu. wt. % solid distribution of liquid products C ₄ = 1C ₆ = C ₆ = c "= C | 0 ~ 6001 Ni (acac) ₂ 0,075 dark brown solution, something solid. substances 0.0094 324 1.52 95.4 4.6 4 65 4 7 9 6002 Ni (diesel) ₂ 0.285 dark brown solution 0,0356 8 0.14 29.5 70.5 74 0 0 4 0 6003 Co (acac) ₂ 0,075 brown solution dark solid substance 0.0094 59 0.28 78.5 21.5 71 13 0 11 1 6004 Mn (acac) ₂ 0,073 brown green solution 0,0091 18 0.08 27.7 72.3 54 0 0 6 0 6005 Mn (acac) ₂ 0,102 brown solution 0.0128 12 0.08 23.7 76.3 50 0 0 0 0 6006 Cu (acac) ₂ 0,076 dark green solution 0.0095 97 0.46 89.2 10.8 5 0 0 0 0 6007 MoO ₂ (acac) 2 0,095 green / red solution, some solids 0.0019 16 0.10 47.7 52.3 41 0 0 34 5 6008 TiO (acac) ₂ 0,075 0.0094 222 1.04 71.2 28.8 11 48 7 8 20 May 6009 VO (acac) ₂ 0,077 - 0.0096 115 0.56 56.8 43.2 15 Dec 50 13 16 2 6010 Zr (acac) ₂ 0.141 - 0.0176 29 0.26 26.8 73.2 0 27 Mar: 0 44 4

The data in Table XXVIII shows that other metal compounds can trimerize, oligomerize and / or polymerize 1-olefins. Of these metal compounds, Ni (acac) 2, experiment 6001, shows the best activity and selectivity in trimerization.

Example VII

In the following example, experiments 7001-7005 demonstrate the effect of alkyl metal hydrolysis prior to use and the presence and absence of pyrrole-containing compounds. Attempts 7006-7009 compared

Experiments 7010-7013 demonstrate the effect of preparing a catalyst system in an unsaturated hydrocarbon.

Experiments 7001-7005

In experiments 7001-7005, the molar ratio of elemental chromium to elemental aluminum of the cligand (Cr: Al: L) in the catalyst components added to the reactor was 1:30:10.

In experiments 7001-7003, the chromium compound is Cr (EH) ₃ and the chromium compound in experiments 7004 and 7005 is Cr (Py) ₃ . The aluminum compound is triisobutylaluminum (Al (i-Bu) ₃ ) and was worked up as follows. About 10 wt. of a solution of triisobutylaluminum in heptane was added at one time with 1.0 mol. equivalent of distilled water, while cooling the vessel containing the solution with ice water to maintain the temperature at about 10 to about 20 ° C. The solution is vigorously stirred during and after the addition of water and stirring is continued until gas evolution is observed. The ligand is dimethoxyethane (DME).

Experiments 7001-7005 were performed in a 21 liter autoclave reactor. The chromium compound was dissolved in 400-500 ml of anhydrous n-heptane and added to the reactor under bubbling dry nitrogen. A suitable volume of stirred, treated 0.31 M Al (i-Bu) ₃ solution in heptane was then added as described above. A suitable volume of DME was then added along with 5 mL of nonane (internal reactor standard). The reactor is sealed and the temperature is raised to 80 ° C in Experiment 7001 and 95 ° C in Experiments 7002-7005 and the pressure is adjusted to 3.8 MPa with ethylene. Ethylene was fed as needed for experiment 25 minutes in experiment 7001, 30 minutes in experiment 7002 and 45 minutes in experiments 7003-7005.

At the end of each experiment, a sample of the liquid reaction product mixture is sampled and analyzed by capillary gas chromatography on an HP-5800 gas chromatography equipped with a FID detector and a 60 m DB-1 column having an internal diameter of 0.25 mm and 0.25 µm film. The gas chromatograph was programmed from 40 to 275 ° C at a rate of 10 ^° C.min -1 with a 20 minute residence time. The remaining reaction product was evaporated and the amount of solid product determined.

The catalyst systems used in experiments 7006-7013 were prepared by the following procedures. Catalyst systems in experiments 7006-7009 were prepared in the presence of toluene, an unsaturated aromatic hydrocarbon. Catalyst systems in experiments 7010-7013 were prepared in the presence of 1-hexene, an unsaturated aliphatic hydrocarbon.

Attempt 7006

3.72 g (Na (DME) ₂ ) (CrCl (Py) ₃ DME) were combined with 50 ml toluene. 26.4 ml of pure (93%) TEA was added slowly and stirred for 30 minutes. The suspension turned dark brown. Excess solvent was removed in vacuo to give a dark, tan oil and a solid. About 70 ml of cyclohexane are added. The resulting product is filtered off and the filtrate is diluted to 200 ml with cyclohexane and 8.0 ml is introduced into the reactor. The product contains 1.67 mg Cr / ml.

Attempt 7007

0.35 chromium (III) ethyl hexanoate (CrEH ₃ ) was combined with about 15 ml toluene to form a dark green solution. 0.22 ml of 2,5-dimethylpyrrole (2,5-DMP) and 0.20 ml of 1-bromobutane are added. 5.7 ml of a 1.9 M TEA solution in toluene are slowly added and stirred for 30 minutes. A greenish brown solution and a solid are obtained. Excess solvent was removed in vacuo and the liquid was extracted into about 15 mL of cyclohexane. The resulting product was filtered off and the filtrate was diluted to 25 ml with cyclohexane to give a golden red solution, 7.0 ml of which was placed in the reactor. The product contains 0.014 g CrEH ₃ / ml.

-25GB 287405 B6

Attempt 7008

The procedure described in Experiment 7007 was repeated except that 0.22 g of CrEH ₃ and 0.13 ml of 2,5-DMP were used. 0.10 ml GeCl ₄ was added instead of 1-bromobutane. Addition of 3.4 ml of a 1.9 Μ TEA solution in toluene yields a brown to brownish-yellow solution and a precipitate. The final product after filtration and dilution to 25 ml with cyclohexane was a bright golden yellow color and contained 0.0088 g CrEH ₃ / ml. 3.0 ml were introduced into the reactor.

Attempt 7009

2.070 g of CrPy ₃ Cl are added to 70 ml of toluene and 62 ml of a 1.9 M TEA solution in toluene, mixed and filtered. The filtrate volume is reduced to about 20 ml by vacuum. The viscous brown solution obtained is filtered again. Then about 30 ml of pentane is added to the filtrate. After about one day, excess solvent was removed in vacuo. 38.1 g of aluminophosphate (P / Al molar ratio 0.9; activation at 700 ° C), prepared according to US 4364855, are then added. The suspension is stirred for about 30 hours. The solid was filtered and washed with toluene, cyclohexane and pentane, each time separately. 0.4388 g of solid catalyst system is introduced into the reactor.

Attempt 7010

0.21 g (Na (DME) ₂ ) (CrCl (Py) ₃ DME) was combined with about 15 ml of 1-hexene. Slowly add 0.75 mL of pure (93%) TEA to form a brown solution and a sticky precipitate, stirring for 30 minutes. Excess solvent was removed in vacuo. The residue is extracted with about 15 ml of cyclohexane, filtered and the filtrate is diluted to 25 ml with cyclohexane. Place 8.0 mL (0.067 g) in the reactor.

Attempt 7011

Experiment 7010 was followed except that the catalyst system (final), in cyclohexane, was aged about 24 hours before use. Place 8.0 mL (0.067 g) in the reactor.

Attempt 7012

Dissolve 0.26 g of CrEH ₃ with your 15 ml of 1-hexene. 0.15 ml of 2,5-DMP and 0.13 ml of 1-bromobutane are added. 1.0 ml of pure (93%) TEA was added slowly and stirred for 30 minutes. Excess solvent was removed in vacuo and the liquid was extracted into about 15 mL of cyclohexane. The resulting product was filtered and the filtrate was diluted to 25 mL with cyclohexane. Place 7.0 mL in the reactor.

Attempt 7013

0.21 g of [Na (DME) ₂ ] [CrCl (Py) ₃ DME] was combined with about 15 ml of 1-hexane. 1.0 ml of pure (93%) TEA is slowly added, forming a dark brown solution and precipitate, and stirred for about 1 hour. The solution was decanted and 1.5 g of aluminophosphate (P / Al molar ratio 0.4; activated at 700 ° C), prepared according to US 4364855, was added.

The supported catalyst system is filtered off, washed with 1-hexene and dried under nitrogen. 0.6328 g of solid catalyst system is introduced into the reactor.

Experiments 7006-7013 were performed in a 1.2 liter autoclave reactor containing cyclohexane. The heterogeneous, dried, supported catalyst systems (experiments 7009 and 7013) are mixed in cyclohexane to facilitate feed to the polymerization reactor and fed to the polymerization reactor in a countercurrent ethylene (CP quality). Homogeneous, liquid, non-carrier catalyst systems (experiments 7006-7008 and 7010-7012) are diluted in cyclohexane and fed to the polymerization reactor in countercurrent ethylene (CP quality). The reactor is sealed and the addition of ethylene is terminated when the reactor temperature is 80 ° C. The ethylene pressure is increased to a total reactor pressure of 3.8 MPa.

-26GB 287405 B6

Ethylene was introduced as needed over the 30 minute duration of the experiment. At the end of the experiment, a sample of the liquid reaction product mixture is sampled and analyzed by capillary gas chromatography on an HP-5880 chromatograph equipped with a FID detector. The DB-1 column used is 60 m long, 0.25 mm internal diameter and 0.25 µm film thickness. The gas chromatograph was programmed from 5-40 ° C to 275 ° C at a rate of 10 ° C / min with a 20 minute residence time. The remaining reaction product was evaporated and the amount of solid product determined.

The results of the reactions are summarized in Table XXIX.

Try cat. system mg Cr (elem.) charge g prod./gCr / h activity gramy prod. tot. % wt. likvid. % wt. solid mol. Cr / N / Al / L ratio ” liquid distribution, product wt. % C ₃ = 1- _C6 = c «= c ₈ = C10 7001 Cr (EH) ₃ . DME, Al (i-Bu) i / H ₂ O 37.6 430 6.8 47 53 1/0/30/10 1 94 <1 4 <1 7002 ^b) Cr (EH) ₃ , DME, ARi-Bu) / H ₂ O 37.6 3,100 59.1 16 84 1/0/30/10 1 94 1 1 2 7003 Cr (EH) ₃ , DME, AR 1 -Bujy H ₂ O 13.2 4,000 39.7 64 36 1/0/30/10 1 95 <1 2 1 7004 Cr (Py) ₃ ^{c >} DME, ARi-BulV H ₂ O 13.5 830 8.3 87 13 1/0/30/10 1 83 6 2 7 7005 Cr (Py) ₃ '> DME, AR 1 -Bu / H ₂ O 38.7 520 15.0 76 24 1/0/30/10 2 80 4 2 6 7006 CrCl (Py) ₃ . DME, TEA 13.5 7,800 52.6 99.4 0.6 1/3/30/0 <1 82 10 1 7 7007 Cr (EH) ₃ 25 DMP TEA n BuBr 9.9 25,300 126.8 99.2 0.8 1/3/15 / 2.5 <1 92 2 <1 5 7008 Cr (EH) ₃ 25 DMP TEA GeCh 2.7 66,400 87.7 99.9 0.1 1/3/15 / 2.5 <1 98 <1 <1 <1 7009 CrCl (Py) ₃ , DME, 0.9 P / Al 0.397 g catalyst 69 " Γ 14.0 97.1 2.9 1/3/30/0 <1 87 7 1 3 7010 CrCl (Py) ₃ , DME, TEA 6 5,200 16.3 96.3 3.7 1/3/15/0 16 55 2 12 8 7011 DMCR, TEA 6 5,070 15.9 96.2 3.8 1/3/15/0 15 Dec 55 2 12 8 7012 Cr (EH) ₃ , 2.5DMP, TEA n-BuBr 7.4 10,200 38.9 96.7 3.3 1/3/15/0 3 74 5 2 12 7013 CrCl (Py) ₃ , DME, TEA 0.4 P / Al 0.6328 g catalyst 34 " Γ 19.0 56.8 43.2 1/3/15 / 2.5 9 45 3 10 10

^and N is a nitrogen-containing compound, i.e. a pyrrole-containing compound, L is a ligand.

^b Reactor clogged with solids.

^c CrCl (Py) ₃ is equivalent to Cr (Py) ₃ , both representing (Na (DME) ₂ ) / CrCl (Py) ₃ DME).

^d Activity expressed in g / product / g catalyst / h.

The data in Table XXIX show that the presence of water (experiments 7001-7005) is detrimental to the formation of liquids such as 1-hexene. In fact, water in the reactor leads to greater solids formation.

-27GB 287405 B6

Experiments 7006-7013 show that catalyst systems prepared in the presence of any unsaturated hydrocarbon are effective in trimerization. However, a comparison of experiments 7010-7013 in toluene with experiments 7010-7013 in 1-hexene shows that the unsaturated aromatic hydrocarbon is the preferred medium for the preparation of the catalyst system.

Example VIII

Experiments 8001-8017 in this example demonstrate the effect of various pyrrole compounds, halogens and metal additives used.

The catalyst systems used in experiments 8001-8017 were all prepared in the same manner. In a typical preparation, chromium (III) -2-ethylhexanoate was dissolved in toluene. Then, 3 equivalents of 2,5-dimethylpyrrole (or hydrogenpyrrolidine in experiments 8014-8017) were added to the solution. Then the desired amount of halide additive (2-3 mol equivalents) was added followed by 15 mol. triethylaluminum equivalents (TEA). The reaction mixture was stirred for 5-10 minutes and toluene was removed in vacuo. The liquid residue was diluted to a total volume of 10 ml with cyclohexane and introduced into the reactor as a catalyst system.

Trimerization experiments were performed in a 21 liter autoclave polymerization reactor containing 1.2 liters of 85% cyclohexane as the reactor diluent. The catalyst system was introduced into the reactor and then cyclohexane was added. The reactor temperature was raised to 80 ° C and ethylene was introduced at this temperature. The pressure was maintained at 40 bar with ethylene addition as needed. Each reaction was carried out for 30 minutes prior to ethylene shutdown. At the end of the experiment, samples were taken and analyzed by gas chromatography as described in other examples.

The results of the experiments are shown in Table XXX, as well as the results of the analyzes.

Table XXX

Try ingredient mgCr batch Mol. Cr / Py / TEA / Ex. Activity, ’g liquid / g Cr / h tot. prod. Gramme. wt. % solid % liquid product distribution, wt. C ₄ = 1- _C6 = C ₆ = C ₈ = Customs ^- 8001 None 13.7 1/3/15/0 4700 33.7 95 5 30 43 6 5 13 8002 DEAC 14.2 1/3/15/3 16800 121.2 99 1 <1 86 3 1 8 8003 DEAB 6.6 1/3/15/3 1800 61.5 98 2 <1 93 2 <1 4 8004 DEA1-I 13.7 1/3/15/3 630 5.0 86 14 4 72 8 2 12 8005 n-BuCl 6.8 1/3/15/3 6300 21.9 98 2 18 52 7 3 16 8006 n-BuBr 6.9 2.5 27500 95.0 > 99 <1 <1 91 2 <1 5 8007 n-BuBr 9.9 2.5 25300 126.8 > 99 <1 <1 92 2 <1 5 8008 n-Bul 6.1 1/3/15/3 2000 7.2 85 15 Dec 4 71 7 2 14 8009 Me ₃ SiCl 14.6 1/3/15/3 3600 26.9 97 3 16 57 6 4 14 8010 Me ₃ SiBr 6.6 1/3/15/3 14000 46.6 > 99 <1 <1 86 4 <1 8 8011 GeCl ₄ 6.6 1/3/15/2 55000 181.7 > 99 <1 <1 96 <1 <1 3 8012 GeCU 2.7 1/3/15/2 66400 87.7 > 99 <1 <1 98 <1 <1 <1 8013 SnCL 6.9 1/3/15/2 40600 140.4 > 99 <1 <1 96 <1 <1 2 8014 DEAC 10.8 2.5 6900 38.5 96 4 <1 87 4 2 5 8015 DEAB 10.8 2.5 2600 14.3 97 3 <1 89 3 2 4 8016 DEAL-I 10.8 2.5 70 0.4 44 56 19 Dec 60 6 3 4 8017 GeCU 10.8 2.5 3300 19.0 94 6 <1 95 2 1 2

^and Based on grams of liquid product only.

The data in Table XXX shows that the selectivity to 1-hexene increases in the order of I <Cl <Br. The bromine-containing additives have the highest selectivity for the formation of 1-hexene as compared to the corresponding chloride or iodide additives. Increasing the production of 1-hexene also means less by-product formation (C ₄ =, C 8 = and C 10 =). The ratio of 1-hexene to internal hexenes also tends to increase in the order of I <Cl <Br. The use of halides leads not only to a larger amount of product but also to a cleaner trimer product. The activity of the catalyst system increases in order

-28GB 287405 B6

I, Cl., Br. However, the activity between Br and Cl analogs cannot be predicted. For some additives (SnX4 and AlX ₃ SiX), Br is more active.

The values in Table XXX also show that the trend in 1-hexene selectivity and activity can be extended to catalysts containing other pyrroles as shown in experiments 8014-8017.

The best combination of activity and selectivity is achieved using GeCl ₄ or SnCl ₄ as the halide additive. It has been found that the selectivity to 1-hexene is also influenced by the ratio of halide additive to triethylaluminum, which makes it possible to obtain high selectivity by other halide additions.

Example IX

In this example, experiments 9001-9004 demonstrate that excess unsaturated aromatic hydrocarbon can be detrimental to trimerization and / or oligomerization. When the catalyst system is prepared in the presence of an aromatic hydrocarbon such as, for example, toluene, it is preferable to remove excess aromatic hydrocarbon. The resulting liquid is then extracted or dissolved in a desired solvent such as cyclohexane or heptane. Without wishing to be bound by theory, it is believed that an aromatic hydrocarbon may compete in a trimerization and / or oligomerization with a monomer such as ethylene at the active sites of the catalyst system. Thus, it is believed that this competition may inhibit the activity of the catalyst system.

The catalyst system used in experiments 9001-9004 was prepared using 1.35 g of chromium (III) 2-ethylhexanoate dissolved in toluene. 0.86 ml (3.2 molar equivalents) of 2,5-dimethylpyrrole was added to the solution. 0.90 ml (3.2 molar equivalents) of n-butyl bromide are then added, followed by 7.60 ml (21 molar equivalents) of 93% triethylaluminum. The mixture was stirred for 5-10 minutes and the toluene was removed in vacuo. The liquid residue was dissolved in 30 ml of cyclohexane, filtered and then diluted to a total volume of 50 ml with additional cyclohexane. Four (4) ml of this solution is then placed together with the required amount of anhydrous, degassed toluene (0, 5, 10 or 15 ml) into the reactor.

Trimerization reaction experiments were carried out in a 21 liter autoclave polymerization reactor containing 1.2 liters of 85% cyclohexane as the reactor diluent. The catalyst system is placed in a reactor with the following addition of cyclohexane. The reactor temperature is raised to 80 ° C and ethylene is then introduced. The pressure is maintained at 38 bar with ethylene feed as needed. Each experiment lasted 30 minutes prior to ethylene shutdown. The total amount of ethylene consumed, ie the feed, was measured.

Experiment 9001-9004 results are shown in Table XXXI.

Table XXXI

Influence of aromatic hydrocarbons on catalyst system activity

Try toluene added, ml Add toluene., vol.% ^and ethylene consumed after 30 min ^b , g 9001 0 0.00 184 9002 5 0.42 160 9003 10 0.83 127 9004 15 Dec 1,25 109

^and Based on the total value of the reactor diluent. ^b Not adjusted for the solubility of ethylene in cyclohexane.

-29GB 287405 B6

The data in Table XXXI shows that the presence of an aromatic hydrocarbon, i.e. toluene, can lead to a significant reduction in catalyst system activity, as measured by ethylene consumption. This reduction is proportional to the amount of aromatic hydrocarbon added to the reactor.

Claims (31)

CLAIMS 1. A process for preparing a catalyst system comprising combining a metal source, a pyrrole-containing compound and an alkyl metal in a co-solvent without a prior reaction step between a metal source and a pyrrole-containing compound in the presence of an electron donor solvent. The process according to claim 1, characterized in that an unsaturated hydrocarbon, optionally providing a common solvent, is also added. 3. The process of claim 2 wherein the unsaturated hydrocarbon is an aromatic or aliphatic hydrocarbon having less than 70 carbon atoms per molecule. 4. A process according to claim 3 wherein the unsaturated hydrocarbon is an aromatic hydrocarbon having less than 20 carbon atoms per molecule. The method of claim 4, wherein the aromatic hydrocarbon is toluene, benzene, xylene, mesitylene or hexamethylbenzene. Process according to any one of claims 2 to 5, characterized in that the excess of the unsaturated aromatic hydrocarbon is evaporated from the resulting catalyst system. 7. The process of claim 3 wherein the unsaturated hydrocarbon is ethylene. Process according to any one of the preceding claims, characterized in that a chromium, nickel, cobalt, iron, molybdenum or copper compound is used as the metal source. Process according to claim 8, characterized in that a chromium compound is used as the metal source. Process according to any one of the preceding claims, characterized in that the pyrrole-containing compound is pyrrole or 2,5-dimethylpyrrolidide. Process according to any one of the preceding claims, characterized in that an aluminum, lithium, magnesium or zinc derivative is used as the alkyl metal. Process according to Claim 11, characterized in that an alkyl aluminum is used as the alkyl metal. The process according to claim 12, wherein the aluminum alkyl is a trialkyl aluminum compound such as triethyl aluminum. Process according to any one of the preceding claims, characterized in that a carrier is introduced into the catalyst system. -30GB 287405 B6 Process according to claim 14, characterized in that the carrier is an inorganic oxide. 16. The process of claim 15 wherein the inorganic oxide is silica, combined silica-alumina, alumina, fluoridated alumina, silane alumina, thorium oxide, aluminophosphate, aluminum phosphate, phosphated silica, phosphated alumina, combined silica-titanium dioxide, co-precipitated silica / titanium dioxide, fluoridated / silated alumina or mixtures thereof. Process according to any one of the preceding claims, characterized in that it is carried out in the presence of an added halide source. Process according to claim 17, characterized in that the halide source is a chloride or bromide source or a mixture thereof. The method of claim 17 or 18, wherein the halide source is a compound of formula RmX _n , wherein R is an organic or inorganic residue, X is a halide, and the sum of m plus n is any number greater than zero. A process according to claim 19, wherein a compound of the formula R _m X _{n is used} , wherein R is aluminum, silicon, germanium, hydrogen, boron, lithium, tin, gallium, indium, lead or a mixture thereof. A process according to claim 20, characterized in that a compound of the formula R _m X _n , wherein R is tin, germanium or a mixture thereof, is used. A process according to any one of the preceding claims, characterized in that the resulting catalyst system has the following relative ratio of (a) 1 mol of metal source metal, (b) 1 to 15 mol of pyrrole-containing compound, (c) 5 to 40 mol and (d) 1 to 30 moles of halide. A method according to any one of the preceding claims, characterized in that it is carried out with the exclusion of oxygen and water. A method according to any one of the preceding claims, characterized in that the metal source and the pyrrole-containing compound are combined prior to the addition of the alkyl metal. A process according to any one of the preceding claims, characterized in that said catalyst system, prepared as a cocatalyst system, is mixed with a polymerization catalyst system. 26. The process of claim 25 wherein the polymerization catalyst system is a system comprising a catalyst comprising chromium, titanium, zirconium and / or vanadium. Use of a catalyst system or a catalyst / cocatalyst system prepared by the process of any one of the preceding claims for trimerization, oligomerization or polymerization of an olefinic compound. Use according to claim 27, wherein the olefinic compound has from 2 to 30 carbon atoms per molecule and at least one olefinic double bond. -31GB 287405 B6 Use according to claim 28, wherein the olefinic compound is ethylene, 1-butene, 1-hexene, 1,3-butadiene or a mixture thereof. Use according to any one of claims 27 to 29, wherein an unsaturated hydrocarbon is attached in the preparation of the catalytic system 5, but the unsaturated hydrocarbon is first introduced during the trimerization, oligomerization or polymerization process. The use of claim 30, wherein the unsaturated hydrocarbon used to prepare the catalyst system is an unsaturated aliphatic hydrocarbon which also acts as an olefinic compound, 10 which is trimerized, oligomerized or polymerized.